Home Physical Sciences Structural aspects of Pt(η3-X1N1X2)(PL) (X1,2 = O, C, or Se) and Pt(η3-N1N2X1)(PL) (X1 = C, S, or Se) derivatives
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Structural aspects of Pt(η3-X1N1X2)(PL) (X1,2 = O, C, or Se) and Pt(η3-N1N2X1)(PL) (X1 = C, S, or Se) derivatives

  • Melník Milan EMAIL logo , Mikušová Veronika and Mikuš Peter EMAIL logo
Published/Copyright: March 22, 2024

Abstract

This article covers 26 Pt(ii) complexes of compositions Pt(η3-X1N1X2)(PL) (X1,2 = O, C, or Se) and Pt(η3-N1N2X1)(PL) (X1 = C, S, or Se). These complexes crystallized in two crystal classes: monoclinic (14 examples) and triclinic (12 examples). The heterotridentate ligand with monodentate PL builds up a distorted square-planar geometry around each Pt(ii) atom. Each heterotridentate ligand Pt(η3-X1N1X2)(PL) creates two metallocyclic rings with a common N1 atom of the O1C2N1C3O2, O1C3N1C3O2, O1C2NN1C3O2, C1C2N1C2C2, and Se1C2N1NC2Se2 types. In Pt(η3-N1N2X1)(PL) complexes, the tridentate ligand with a common N2 atom forms the following types of metallocyclic rings: N1C2N2C2C1, N1C2N2NCS1, and N1CNN2NCSe1. The total mean values of τ4 for respective complexes as it grows in the sequence: 0.056 (Pt(η3-O1N1O2)(PL)) < 0.091 (Pt(η3-Se1N1Se2)(PL)) < 0.161 (Pt(η3-N1N2S1)(PL)) < 0.174 (Pt(η3-N1N2Se1)(PL)) < 0.188 (Pt(η3-C1N1C2)(PL)) < 0.211 (Pt(η3-N1N2C1)(PL)). The distortion of the square-planar geometry increases in the given sequences. The structural data (Pt–L, L–Pt–L) are analyzed and discussed with attention to the distortion of a square-planar geometry about the Pt(ii) atoms as well as of trans-influence.

Graphical abstract

Structure of [Pt(η3-C22H11F6N3O2)(PPh3)]

List of abbreviations

C10H10N5S

(N-(1-(1H-benzimidazol-2-yl)ethylidene)carbamohydrazonothiolato)

C12H11F6N3O2

(2,2′-(3,5-bis(trifluoromethyl)phenyl)-1H-1,2,4-triazole-3,5-diyl)

C12H16N2O4Se2

diethyl-3,3′-(diazone-1,2-diyl-N)bis(2-(hydroseleno)but-2-enoatato)

C13H11ClN6OS

(N-(1-(3-acetyl-1H-1,2,4-triazol-5-yl)ethylidene)-N-(4-chlorphenyl) carbamohydrazonothiolato)

C13H12N6OS

(N-(1-(3-acetyl-1H-1,2,4-triazol-5-yl)ethylidene)-N-phenylcarbamohydrazonothiolato)

C13H9NO2

N(α,α′-dioxobenzylidene) anilinate

C14H10N2O3

2-2′-carboxylatophenylazo-4-methylphenolate

C14H10N3

(2-(6-(1H-imidazol-5-yl)pyridine-2-yl)phenyl)

C14H10N3

(2-(6-(3-1H-pyrazolyl)-2-pyridyl)phenyl)

C17H11N

2,2′-(pyridine-2,6-diyl)diphenyl

C17H14F2N4

(2-(6-(5-t-butyl-1,2,4-triazol-2id-3-yl)pyridine-2-yl)-3,5-difluorophenyl)

C17H9F2N

(2,2′-(pyridine-2,6-diyl)bis(5-fluorophenyl))

C17H9F2N

(2,2′-pyridine-2,6-diyl)bis(5-fluorobenzenide)

C18H11F2N

(2-(4-fluoro-2-methylphenyl)-6-(4-fluorophenyl)pyridine)

C18H11F2N

(5-fluoro-2-{6-(fluorobenzene-2-diyl)pyridine-2-yl}-methylbenzenide)

C20H15NO2

(2,6-bis(O-phenylene)-4-ethoxycarbonylpyridine)

C24H20N3

(2-(4-(4-dimethylaminophenyl)-2,2′-bipyridin-6-yl)phenyl)

C28H23N2

(3-(4-t-butyl-8-(isoquinolin-3-yl)pyridine-2-yl)-2-naphtyl)

C28H24N4S2

PhSNC(MeC6H4)N-NC(MeC6H4)NSPh

C30H19N2

(3-(4-phenyl-6-(isoquinolin-3-yl)pyridine-2-yl)-2-naphtyl)

CL

ligand coordinated via the C atom

m

monoclinic

NL

ligand coordinated via the N atom

OL

ligand coordinated via the O atom

P(C14H19O5)(Ph2)

benzo-15-crown[5] diphenylphosphine

P(CH2Et)3

tri-n-propylphosphine

P(CH2Ph)3

tribenzylphosphine

P(tolyl)3

tris(2-methylphenyl)phosphine

Pcy3

tricyclohexylphosphine

PL

ligand coordinated via the P atom

PMe3

trimethylphosphine

PPh3

triphenylphosphine

tfh

tetrahydrofuran

tr

triclinic

1 Introduction

Organophosphines as soft P donor ligands are very useful for building a wide variety of platinum complexes. Research activity in this field is always very active. Much attention is paid to heterotridentate organomonophosphines as ligands. Recently, we analyzed and classified structural data of monomeric Pt(ii) complexes in which a distorted square-planar geometry about each Pt(ii) atom is built up by heterotridentate organomonophosphine with monodentate Y ligands: Pt(η3-P1N1N2)(Y), Pt(η3-P1N1X1)(Y) (X1 = O1, C1, S1, or Se2); Pt(η3-N1P1N2)(Cl); Pt(η3-S1P1S2)(Cl); Pt(η3-P1S1Cl1)(Y); and Pt(η3-P1Si1N1)(OL) [1].

Structural data of monomeric Pt(ii) complexes of the compositions: Pt(η3-P1C1C2)(Y) (Y = NL or I) and Pt(η3-P1C1N1)(Y) (Y = OL, NL, CL, Cl, or Br) were also analyzed and classified [2]. There are several monomeric Pt(ii) complexes where the inner coordination sphere is built up by the homotridentate ligand with monodentate organomonophosphine of the composition: Pt(η3-X1X2X3)(PL) (X = N, S, or Te). Their structural data were also analyzed and classified [3].

The chemistry of platinum complexes is important in the fields of biochemistry, catalysis, and theory. The complexes presented in the article were used predominantly in catalytic processes or theoretical studies. This study aims to analyze and classify the structural data of Pt(η3-X1N1X2)(PL) (X1,2 = O, C, or Se) and Pt(η3-N1N2X1)(PL) (X1 = C, S, or Se).

2 Structural aspects of Pt(η3-X1N1X2)(PL) and Pt(η3-N1N2X1)(PL) derivatives

There are 26 complexes that are based on heterotridentate ligands, and they can be divided into two groups, one of the compositions Pt(η3-X1N1X2)(PL), where (X1, X2 = O1, O2; C1, C2; or Se1, Se2), and the other Pt(η3-N1N2X1)(PL) (X1 = C1, S1, or Se1). Their structural data are given in Tables 1 and 2, respectively. Structural data used in this study for discussion and calculations were obtained from the Cambridge Crystallographic Database (CCDB).

Table 1

Structural data for Pt(η3-X1N1X2)(PL) derivatives (X1, X2 = O1, O2; C1, C2; or Se1, Se2)a

Complex Pt(η3-X1N1X2)(PL) Crystal cl.Space gr. z a (Å)b (Å)c (Å) α (°)β (°)γ (°) Chromophore(chelate rings)τ4b Pt–Lc(Å) L–Pt–Lc (°) Ref.
[Pt{η3-C13H9NO2-O1N1O2}⸱ (PPh3)] m 15.721(4) 106.05(2) PtO2NP O1 1.975(9) O1, N1 82.4(4)d [4]
P21/n 9.106(2) (O1C2N1C3O2) N1 2.064(12) N1, O2 94.8(4)e
4 18.500(5) 0.081 O2 1.996(9) O1, O2 176.1(4)
P 2.248 O1, P 91.5(3)
O2, P 91.5(3)
N1, P 172.4
[Pt{η3-C22H11F6N3O2-O1N1O2}⸱(PPh3)] tr 9.418(0) 81.75(0) PtO2NP O1 1.994 O1, N1 90.6e [5]
(at 173 K) P 1 ¯ 13.069(0) 88.58(0) (O1C3N1C3O2) N1 2.021 N1, O2 90.2e
2 14.123(0) 80.29(0) 0.028 O2 2.004 O1, O2 179.0
P 2.256 O1, P 90.6
O2, P 87.5
N1, P 177.0
[Pt{η3-C14H10N2O3-O1N1O2}⸱(PPh3)] tr 8.928(0) 73.64(0) PtO2NP O1 1.995 O1, N1 88.2e [6]
(at 150 K) P 1 ¯ 12.223(0) 83.72(0) (O1C2NN1C3O2) N1 2.000 N1, O2 92.0e
2 14.145(0) 69.36(0) 0.06 O2 1.988 O1, O2 176.5
P 2.251 O1, P 89.0
O2, P 90.7
N1, P 175.0
[Pt{η3-C17H9F2N-C1N1C2}·{P(o-tolyl)3}]·CHCl3 m 36.465(0) 104.09(0) PtC2NP C1 2.085 C1, N1 79.8d [7]
C21/c 8.393(0) (C1C2N1C2C2) N1 2.024 C2, N1 79.5d
(at 150 K) 8 23.214(0) 0.168 C2 2.094 C1, C2 158.9
P 2.255 C1, P 103.1
C2, P 97.5
N1, P 177.3
[Pt{η3-C18H11F2N-C1N1C2}·{P(CH2Ph) 3}]·1.4CHCl3 m 14.619(0) 98.64(0) PtC2NP C1 2.062 C1, N1 79.9d [8]
P21/a 17.398(0) (C1C2N1C2C2) N1 2.029 C2, N1 80.2d
(at 150 K) 4 28.629(0) 0.282 C2 2.071 C1, C2 158.8
P 2.241 C1, P 102.2
C2, P 98.7
N1, P 169.8
[Pt{η3-C17H9F2N-C1N1C2}⸱{P(CH2Ph)3}] tr 12.121(0) 68.82(0) PtC2NP C1 2.075 C1, N1 79.8d [7]
(at 150 K) P 1 ¯ 12.191(0) 69.92(0) (C1C2N1C2C2) N1 2.033 C2, N1 80.0d
2 12.273(0) 64.64(0) 0.242 C2 2.085 C1, C2 159.2
P 2.228 C1, P 103.8
C2, P 96.9
N1, P 168.7
[Pt{η3-C18H11F2N-C1N1C2}·{P(CH2Et)3}] m 9.962(0) 100.22(0) PtC2NP C1 2.056 C1, N1 79.9d [9]
(at 150 K) P21/c 9.222(0) (C1C2N1C2C2) N1 2.027 C2, N1 80.5d
4 27.300(0) 0.186 C2 2.074 C1, C2 159.8
P 2.299 C1, P 102.1
C2, P 97.7
N1, P 174.2
[Pt{η3-C17H9F2N-C1N1C2}·(PMe3)] m 23.994(0) 107.33(0) PtC2NP C1 2.070 C1, N1 79.5d [10]
(at 150 K) C21/c 12.511(0) (C1C2N1C2C2) N1 2.005 C2, N1 80.2d
4 12.169(0) 0.223 C2 2.065 C1, C2 158.5
P 2.243 C1, P 92.0
C2, P 102.5
N1, P 170.0
[Pt{η3-C17H11N-C1N1C2}·(PPh3)] m 13.958(0) 95.68(0) PtC2NP C1 2.073 C1, N1 79.7d [11]
(at 100 K) P21/c 9.423(0) (C1C2N1C2C2) N1 2.049 C2, N1 80.2d
4 20.659(0) 0.222 C2 2.074 C1, C2 158.8
P 2.241 C1, P 103.0
C2, P 98.7
N1, P 169.8
[Pt{η3-C20H15NO2-C1N1C2}·(PPh3)] m 17.866(0) 101.97(0) PtC2NP C1 2.075 C1, N1 79.8d [12]
(at 150 K) P21/c 17.138(0) (C1C2N1C2C2) N1 2.007 C2, N1 80.4d
4 9.758(0) 0.213 C2 2.073 C1, C2 159.0
P 2.252 C1, P 93.2
C2, P 103.2
N1, P 171.0
[Pt{η3-C17H11N-C1N1C2}·{P(η1-C14H19O5)(Ph)2}]CH2Cl2 tr 9.114(1) 83.56(1) PtC2NP C1 2.082 C1, N1 79.4d [13]
(at 100 K) P 1 ¯ 20.627(2) 82.70(1) (C1C2N1C2C2) N1 2.033 C2, N1 80.1d
4 22.024(2) 88.67(1) 0.219 C2 2.083 C1, C2 157.3
P 2.227 C1, P 100.6
C2, P 101.0
N1, P 171.8
[Pt{η3-C12H16N2O4Se2-Se1N1Se2}·(PPh3)] m 9.259(0) 110.61(0) PtSe2NP Se1 2.394 Se1, N1 83.3d [14]
P21/c 15.525(0) (Se1C2N1NC2Se2) N1 2.078 N1, Se2 98.3e
4 23.892(0) 0.091 Se2 2.349 Se1, Se2 176.3
P 2.259 Se1, P 87.2
Se2, P 90.7
N1, P 170.9

aThe mean value is tabulated when more than one chemically equivalent distance or angle is present. The first number in parentheses is the e.s.d. and the second is the maximum deviation from the mean value. bParameter τ4 – degree of distortion of square-planar geometry. cThe chemical identity of the coordinated atom or ligand is specified in these columns. dFive-membered metallocyclic ring, eSix-membered metallocyclic ring.

Table 2

Structural data for Pt(η3-N1N2X1)(PL) derivativesa (X1 = C1, S1, Se1)a

Complex Pt(η3-N1N2X1)(PL) Crystal cl. space gr. z a (Å) α (°) Chromophore (chelate rings) Pt–Lc (Å) L–Pt–Lc (°) Ref.
b (Å) β (°) τ4 b
c (Å) γ (°)
[Pt{η3-C14H10N3-N1N2C1}·(PPh3)]ClO4 trP 1 ¯ 2 9.406(0) 70.95(0) PtN2CP (N1C2N2C2C1) N1 2.124 N1, N2 78.2d [15]
(at 173 K) 12.549(0) 73.13(0) 0.168 N2 2.022 N2, C1 80.6d
13.139(0) 79.99(0) C1 2.018 N1, C1 158.8
P 2.243 N1, P 103.2
C1, P 97.1
N2, P 177.5
[Pt{η3-C14H10N3-N1N2C1}·(PPh3)]ClO4 trP 1 ¯ 2 9.198(0) 91.57(0) PtN2CP (N1C2N2C2C1) N1 2.101 N1, N2 78.5d [15]
(at 193 K) 9.511(0) 92.52(0) 0.178 N2 2.025 N2, C1 81.1d
16.467(0) 92.95(0) C1 2.005 N1, C1 159.1
P 2.227 N1, P 103.0
C1, P 97.6
N2, P 175.8
[Pt{η3-C28H23N2-N1N2C1}·(Pcy3)]ClO4·2CH3CN mP21/n4 16.423(3) PtN2CP (N1C2N2C2C1) N1 2.103 N1, N2 78.5d [16]
(at 253 K) 17.976(4) 110.42(3) 0.307 N2 2.023 N2, C1 79.7d
17.270(4) C1 2.054 N1, C1 156.4
P 2.283 N1, P 101.6
C1, P 102.4
N2, P 160.3
[Pt{η3-C30H19N2-N1N2C1}·(Pcy3)]ClO4·0.5 CH3CN mC21/c4 26.188(5) PtN2CP (N1C2N2C2C1) N1 2.154 N1, N2 77.8d [16]
(at 253 K) 14.708(3) 99.88(3) 0.266 N2 2.029 N2, C1 80.5d
24.052(5) C1 2.042 N1, C1 156.6
P 2.297 N1, P 103.3
C1, P 99.8
N2, P 165.9
[Pt{η3-C30H19N2-N1N2C1}·(PPh3)]ClO4·MeOH trP 1 ¯ 2 10.713(2) 71.77(3) PtN2CP (N1C2N2C2C1) N1 2.133 N1, N2 77.6d [16]
(at 253 K) 13.300(3) 75.45(3) 0.203 N2 1.975 N2, C1 81.1d
16.081(3) 77.53(3) C1 2.000 N1, C1 158.4
P 2.243 N1, P 105.1
C1, P 96.3
N2, P 173.0
[Pt{η3-C17H14F2N4-N1N2C1}·(PPh3)]thf trP 1 ¯ 2 10.215(0) 96.11(0) PtN2CP (N1C2N2C2C1) N1 2.076 N1, N2 78.3d [17]
(at 223 K) 10.881(0) 104.36(0) 0.179 N2 2.033 N2, C1 80.7d
15.715(0) 104.29(0) C1 2.027 N1, C1 158.8
P 2.241 N1, P 104.2
C1, P 96.8
N2, P 176.0
[Pt{η3-C24H20N3-N1N2C1}·(PPh3)]ClO4 trP 1 ¯ 2 8.526(2) 101.27(0) PtN2CP (N1C2N2C2C1) N1 2.147 N1, N2 77.8d [18]
(at 113 K) 10.015(3) 101.72(0) 0.184 N2 2.022 N2, C1 80.9d
21.052(6) 90.23(0) C1 2.022 N1, C1 158.2
P 2.246 N1, P 106.1
C1, P 95.3
N2, P 175.8
[Pt{η3-C14H10N3-N1N2C1}·(PPh3)]ClO4 mP21/n4 15.135(1) PtN2CP (N1C2N2C2C1) N1 2.130 N1, N2 79.0d [19]
10.811(0) 93.06(0) 0.202 N2 2.029 N2, C1 81.0d
17.558(1) C1 2.005 N1, C1 157.4
P 2.242 N1, P 101.8
C1, P 100.6
N2, P 174.1
[Pt{η3-C10H10N3S-N1N2S1}·(PPh3)]Cl·CH3CN·H2O mP21/n4 10.505(5) PtN2SP (N1C2N2NCS1) N1 2.092 N1, N2 78.8d [20]
21.722(5) 95.11(0) 0.145 N2 2.057 N2, S1 83.5d
14.104(5) S1 2.249 N1, S1 162.3
P 2.257 N1, P 103.5
S1, P 94.2
N2, P 177.2
[Pt{η3-C13H11ClN6OS-N1N2S1}·(PPh3)]Me2SO trP 1 ¯ 2 9.037(0) 103.87(0) PtN2SP (N1C2N2NCS1) N1 2.029 N1, N2 79.0d [21]
14.343(0) 101.62(0) 0.148 N2 2.039 N2, S1 82.9d
15.183(0) 105.96(0) S1 2.261 N1, S1 161.9
P 2.251 N1, P 99.7
S1, P 90.4
N2, P 177.3
[Pt{η3-C13H12N6OS-N1N2S1}·(PPh3)]Me2SO trP 1 ¯ 2 9.195(0) 70.20(0) PtN2SP (N1C2N2NCS1) N1 2.022 N1, N2 79.0d [22]
13.929(0) 76.73(0) 0.15 N2 2.031 N2, S1 83.1d
14.943(0) 73.55(0) S1 2.258 N1, S1 162.1
P 2.250 N1, P 97.9
S1, P 100.1
N2, P 176.7
[Pt{η3-C20H31N9S2-N1N2S1}·(PPh3)]EtOH trP 1 ¯ 2 10.769(5) 81.09(2) PtN2SP (N1C2N2NCS1) N1 2.042 N1, N2 79.0d [23]
(at 100 K) 12.054(5) 89.09(6) 0.184 N2 2.000 N2, S1 82.0d
17.499(5) 70.97(1) S1 2.270 N1, S1 161.0
P 2.268 N1, P 100.0
S1, P 96.0
N2, P 173.0
[Pt{η3-C28H24N4S2-N1N2S1}·(PPh3)].0.5thf mP21/c4 14.234(5) PtN2SP (N1CNN2NCS1) N1 2.031(8) N1, N2 78.5(4)d [24]
18.922(3) 105.19(2) 0.179 N2 1.987(7) N2, S1 81.6(2)d
16.032(3) S1 2.266(3) N1, S1 162.2(2)
P 2.279(3) N1, P 99.9(2)
S1, P 99.7(1)
N2, P 172.5(2)
[Pt{η3-C28H24N4Se2-N1N2Se1}·(PPh3)]⸱Et2O mP21/c4 14.410(1) 105.72(1) PtN2SeP (N1CNN2NCSe1) N1 2.020(1) N1, N2 78.7(4)d [25]
19.003(3) 0.174 N2 1.980(1) N2, Se1 82.3(3)d
16.169(2 Se1 2.368(2) N1, Se1 162.0
P 2.272(4) N1, P 100.0(3)
Se1, P 98.6(1)
N2, P 173.4(1)

aThe mean value is tabulated when more than one chemically equivalent distance or angle is present. The first number in parentheses is the e.s.d. and the second is the maximum deviation from the mean value, bParameter τ4 – degree of distortion of square-planar geometry, cThe chemical identity of the coordinated atom or ligand is specified in these columns, dFive-membered metallocyclic ring.

In the first step, Pt–L bond distances as well as L–Pt–L angles (cis, trans) were identified from the structures registered in the CCDB via program Diamond. In the second step, the sum of covalent radii was calculated from known values of covalent radii of particular atoms in the complexes. In the third step, distortion of the square-planar geometry by parameter τ4 was calculated according to the formula τ 4 = 360 ( α + β ) 141 , where α and β are trans angles in the complexes. Finally, these published and calculated data were compared and discussed for particular complexes within the two above-mentioned groups and their subgroups to find relevant structural trends.

2.1 Pt(η3-X1N1X2)(PL) derivatives

There are 12 examples of such a type, and the structural data are given in Table 1. In three complexes, one monoclinic [Pt(η3-C13H9NO2)(PPh3)] [4] and two triclinic [Pt(η3-C22H11F6N3O2)(PPh3)] (at 173 K) [5] and [Pt(η3-C14H10N2O3)(PPh3)] (at 150 K) [6], heterotridentate ligands via O1N1O2 donor atoms and monodentate PPh3 ligands build up a distorted square-planar geometry about each Pt(ii) atom. The structure of [Pt(η3-C22H11F6N3O2)(PPh3)] [5] is shown in Figure 1 as an example. Each chelate ligand forms two metallocyclic rings with the common N1 atom of the O1C2N1C3O2 (monoclinic), O1C3N1C3O2 (triclinic), and O1C2NN1C3O2 (triclinic) types. The values of the respective chelate O1–Pt–N1/N1–Pt–O2 angles are 82.4/94.8° (monoclinic), 90.6/90.2° (triclinic), and 88.2/92.0° (triclinic).

Figure 1 
                  Structure of [Pt(η3-C22H11F6N3O2)(PPh3)] [5].
Figure 1

Structure of [Pt(η3-C22H11F6N3O2)(PPh3)] [5].

The remaining L–Pt–L bond angles open in the order (mean values): 89.9 (±2.4)° (O2–Pt–P) < 90.4 (±1.4)° (O1–Pt–P) < 174.8 (±2.2)° (N1–Pt–P) < 177.2 (±1.8)° (O1–Pt–O2). The Pt–L bond distance elongates in the sequence (mean values): 1.988 (±0.004) Å (Pt–O1, trans to O2) < 1.996 (±0.008) Å (Pt–O2) < 2.028 (±0.036) Å (Pt–N1, trans to P) < 2.251 (±0.005) Å (Pt–P).

In the following eight complexes: monoclinic [Pt(η3-C17H9F2N)({P(o-tolyl)3}]⸱CHCl3 (at 150 K) [7], monoclinic [Pt(η3-C18H11F2N) {P(CH2Ph)3}]·14CHCl3 (at 150 K) [8], triclinic [Pt(η3-C17H9F2N){P(CH2Ph)3}] (at 150 K) [8], monoclinic [Pt(η3-C18H11F2N) {P(CH2Et)3}] (at 150 K) [9], monoclinic [Pt(η3-C17H9F2N)(PMe3)] (at 150 K) [10], monoclinic [Pt(η3-C17H11N)(PPh3)] (at 100 K) [11], monoclinic [Pt(η3-C20H15NO2)(PPh3)] (at 150 K) [12], and triclinic [Pt(η3-C17H11N){P(η1-C14H19O5)(Ph)2}]·CH2Cl2 (at 150 K) [13]; each heterotridentate ligand via C1N1C2 donor atoms with monodentate PL donor ligand creates a distorted square-planar geometry about each Pt(ii) atom. Each chelate ligand forms a pair of five-membered metallocycles with a common N1 atom of the C1C2N1C2C2 type with the mean values of C1–Pt–N1 and N1–Pt–C2 angles 79.7(±0.3)° and 80.1(±0.4)°, respectively. The mean values of the remaining values of L–Pt–L bond angles open in the order: 98.4(±2.6)° (C2–Pt–P) < 102.3(±1.7)° (C1–Pt–P) < 158.8(±1.5)° (C1–Pt–C2) < 171.8(±3.1)° (N1–Pt–P). The Pt–L bond distance (mean value) elongates in the sequence 2.036(±0.013) Å (Pt–N1, trans to P) < 2.072(±0.013) Å (Pt–C1, trans to C2) < 2.080(±0.014) Å (Pt–C2) < 2.248(±0.046) Å (Pt–P, trans to N1).

The structure of monoclinic [Pt(η3-C12H16N2O4Se2)(PPh3)] [14] is shown in Figure 2. The heterotridentate Se1N1Se2 donor ligand with monodentate PPh3 ligand builds up a distorted square-planar geometry about the Pt(ii) atom. The chelate ligand creates five- and six-membered metallocycles with a common N1 atom of the Se1C2N1NC2Se2 type. The values of Se1–Pt–N1 and N1–Pt–Se1 angles are 83.3° and 98.3°. The remaining L–Pt–L bond angles open in the order: 87.2° (Se1–Pt–P) < 90.7° (Se2–Pt–P) < 170.9° (N1–Pt–P) < 176.3° (Se1–Pt–Se2). The Pt–L bond distance elongates in the sequence: 2.078 Å (Pt–N1, trans to P) < 2.259 Å (Pt–P) < 2.349 Å (Pt–Se2, trans to Se1) < 2.394 Å (Pt–Se1) (Table 1).

Figure 2 
                  Structure of [Pt(η3-C12H16N2O4Se2)(PPh3)] [14].
Figure 2

Structure of [Pt(η3-C12H16N2O4Se2)(PPh3)] [14].

2.2 Pt(η3-N1N2X1)(PL) (X1 = C1, S1, or Se1) derivatives

Structural data for these complexes are displayed in Table 2. In eight complexes, triclinic [Pt(η3-C14H10N3)(PPh3)]ClO4 (at 173 K) [15], triclinic [Pt(η3-C14H10N3) (PPh3)]ClO4 (at 273 K) [15], monoclinic [Pt(η3-C28H23N2)(Pcy3)]ClO4⸱2CH3CN (at 253 K) [16], monoclinic [Pt(η3-C30H19N2)(Pcy3)]ClO4⸱0.5CH3CN [16], triclinic [Pt(η3-C30H19N2)(PPh3)]ClO4⸱MeOH (at 253 K) [16], triclinic [Pt(η3-C17H14F2N4)(PPh3)]thf (at 223 K) [17], triclinic [Pt(η3-C24H20N3)(PPh3)]ClO4 (at 113 K) [18], and monoclinic [Pt(η3-C14H10N3)(PPh3)]ClO4 [19], each heterotridentate ligand via N1N2C1 donor atoms with monodentate PL ligand builds up a distorted square-planar geometry about the Pt(ii) atom. Each heterotridentate ligand creates a pair of five-membered metallocycles with a common N2 atom of the N1C2N2C2C1 type. The N1–Pt–N2 and N2–Pt–C1 bond angles (mean values) are 78.2(±0.5)° and 80.7(±1.0)°. The remaining L–Pt–L bond angles (mean values) open in the order 98.3(±4.1)° (C1–Pt–P) < 103.5(±2.6)° (N1–Pt–P) < 157.9(±1.5)° (N1–Pt–C1) < 172.3(±7.5)° (N2–Pt–P). The Pt–L bond distance elongates (mean values) in the sequences: 2.020(±0.045) Å (Pt–N2, trans to P) < 2.022(±0.032) Å (Pt–C1, trans to N1) < 2.124(±0.048) Å (Pt–N1, trans to C1) < 2.252(±0.045) Å (Pt–P, trans to N2).

The heterotridentate ligands coordinated via N1N2S1 donor atoms with monodentate PPh3 build up a distorted square-planar geometry about each Pt(ii) atom. There are five such complexes: monoclinic [Pt(η3-C10H10N5S)(PPh3)]Cl⸱MeCN⸱H2O [20], triclinic [Pt(η3-C13H11ClN6OS)(PPh3)]Me2SO [21], triclinic [Pt(η3-C13H12N6OS) (PPh3)]Me2SO [22], triclinic [Pt(η3-C20H31N9S2)(PPh3)]EtOH (at 100 K) [23], and monoclinic [Pt(η3-C28H24N4S2)(PPh3)]⸱0.5thf [24]. The structure of [Pt(η3-C10H10N5S)(PPh3)]+ [20] is shown in Figure 3 as an example. Each heterotridentate ligand in these complexes creates two five-membered metallocycles with a common N2 atom of the N1C2N2C2S1 [20,21,22], N1C2N2NCS1 [23], and N1CNN2NCS1 [24] types. The mean values of N1–Pt–N2 and N2–Pt–S1 bond angles are 78.8(±0.3)° and 82.6(±1.4)°. The remaining L–Pt–L bond angles (mean values) open in the sequence: 69.0(±3.8)° (S1–Pt–P) < 99.8(±3.6)° (N1–Pt–P) < 161.5(±1.8)° (N1–Pt–S1) < 175.3(±2.8)° (N2–Pt–P). The Pt–L bond distance (mean values) elongates in the order: 2.022(±0.035) Å (Pt–N2, trans to P) < 2.049(±0.043) Å (Pt–N1, trans to S1) < 2.260(±0.010) Å (Pt–S1) < 2.262(±0.018) Å (Pt–P) (Table 2).

Figure 3 
                  Structure of [Pt(η3-C10H10N5S)(PPh3)]+ [20].
Figure 3

Structure of [Pt(η3-C10H10N5S)(PPh3)]+ [20].

The structure of [Pt(η3-C28H24N4Se2)(PPh3)]⸱Et2O [25] is shown in Figure 4. This is the only example with heterotridentate ligand coordinated via N1N2Se1 donor atoms. Monodentate PPh3 completed a distorted square-planar geometry about the Pt(ii) atom. The heterotridentate ligand forms two five-membered metallocyclic rings of the N1CNN2NCSe1 type. The values of N1–Pt–N2 and N2–Pt–Se1 bond angles are 78.7(4)° and 82.3(3)°, respectively. The remaining L–Pt–L bond angles open in the order: 98.6(1)° (N1–Pt–P) < 100.0(3)° (Se1–Pt–P) < 162.0° (N1–Pt–Se1) < 173.4(1)° (N2–Pt–P). The Pt–L bond distance elongates in the order: 1.980(1) Å (Pt–N2, trans to P) < 2.020(1) Å (Pt–N1, trans to Se1) < 2.272(4) Å (Pt–P) < 2.368(2) Å (Pt–Se1) (Table 2).

Figure 4 
                  Structure of [Pt(η3-C28H24N4Se2)(PPh3)] [25].
Figure 4

Structure of [Pt(η3-C28H24N4Se2)(PPh3)] [25].

3 Conclusions

This structural study includes 26 monomeric Pt(ii) coordination complexes with compositions of Pt(η3-X1N1X2) (PL) (X1,2 = O1,O2; C1,C2; or Se1, Se2) and Pt(η3-N1N2X1) (PL) (X1 = C1,S1, or Se1). These complexes crystallized in two crystal classes: monoclinic (14 examples) and triclinic (12 examples). The variable combination of donor atoms of heterotridentates which with PL build up Pt(η3-X1N1X2)(PL) and Pt(η3-N1N2X1)(PL) can be divided into two sub-groups. In each sub-group, the Pt–L bond distances (mean values) with sums of Pt–L(x4) bond distances are

3.1 Pt(η3-X1N1X2)(PL)

Pt(η3-O1N1O2)(PL): 1.986 Å (Pt–O1); 2.043 Å (Pt–N1); 1.996 Å (Pt–O2); 2.252 Å (Pt–P); Σ 8.28 Å [4,5,6]; Σ 3.27 Å, covalent radius.

Pt(η3-C1N1C2)(PL): 2.072 Å (Pt–C1); 2.036 Å (Pt–N1); 2.080 Å (Pt–C2); 2.248 Å (Pt–P); Σ 8.436 Å [7,8,9,10,11,12,13]; Σ 3.35 Å, covalent radius

Pt(η3-Se1N1Se2)(PL): 2.394 Å (Pt–Se1); 2.078 Å (Pt–N1); 2.349 Å (Pt–Se2); 2.259 Å (Pt–P); Σ 8.98 Å [14]; Σ 4.13 Å, covalent radius.

3.2 Pt(η3-N1N2X1)(PL)

Pt(η3-N1N2C1)(PL): 2.124 Å (Pt–N1); 2.020 Å (Pt–N2); 2.022 Å (Pt–C1); 2.25 Å (Pt–P); Σ 8.418 Å [15,16,17,18,19]; Σ 3.33 Å, covalent radius;

Pt(η3-N1N2S1)(PL): 2.043 Å (Pt–N1); 2.028 Å (Pt–N2); 2.258 Å (Pt–S1); 2.259 Å (Pt–P); Σ 8.588 Å [20,21,22,23,24]; Σ 3.58 Å, covalent radius;

Pt(η3-N1N2Se1)(PL): 2.020 Å (Pt–N1); 1.98 Å (Pt–N2); 2.363 Å (Pt–Se1); 2.272 Å (Pt–P); Σ 8.640 Å [25]; Σ 3.72 Å, covalent radius.

As expected, the sums of respective Pt–L (×4) bond distances grow with a covalent radius of coordinated donor atoms. The Pt–L bond distance in Pt(η3-X1N1X2) (PL) derivatives elongates in the orders (mean values):

Pt–X1(trans to X2): 1.985 Å (X1,2 = O) < 2.072 Å (X1,2 = C) < 2.394 Å (X1,2 = Se);

Pt–X2(trans to X1): 2.000 Å (X1,2 = O) < 2.080 Å (X1,2 = C) < 2.349 Å (X1,2 = Se);

Pt–N1(trans to P, when X1,2 are): 2.036 Å (C) < 2.043 Å (O) < 2.078 Å (Se);

Pt–P (trans to N1, when X1,2 are): 2.248 Å (C) < 2.252 Å (O) < 2.259 Å (Se).

In Pt(η3-N1N2X1) (PL) derivatives, the Pt–L bond distance elongates in the orders (mean value):

Pt–N1(trans to X1, when X1 is): 2.020 Å (X1 = Se) < 2.043 Å (S) < 2.124 Å (C);

Pt–N2(trans to P, when X1 is): 1.982 Å (X1 = Se) < 2.020 Å (C) < 2.028 Å (S);

Pt–X1(trans to N1, when X1 is): 2.022 Å (C) < 2.258 Å (S) < 2.368 Å (Se);

Pt–P (trans to N2, when X1 is): 2.252 Å (X1 = C) < 2.259 Å (S) < 2.272 Å (Se).

These orders correspond quite well with the trans-influence of the respective donor atoms.

The heterotridentate ligands create variates of the metallocyclic rings. Each of these ligands forms two metallocyclic rings with a common N1 atom in Pt(η3-X1N1X2) (PL) derivatives and an N2 atom in Pt(η3-N1N2X1) (PL). In Pt(η3-X1N1X2) (PL) derivatives, the respective chelate L–Pt–L angles are of the types

5 + 5-membered: C1C2N1C2C2 79.7° (C1–Pt–N1) and 80.1° (N1–Pt–C2);
5 + 6-membered: O1C2N1C3O2 82.4° (O1–Pt–N1) and 94.8° (N1–Pt–O2);
5 + 6-membered: Se1C2N1NC2Se2 83.3° (Se1–Pt–N1) and 98.3° (N1–Pt–Se2);
6 + 6-membered: O1C3N1C3O2 90.6° (O1–Pt–N1) and 90.2° (N1–Pt–O2);
6 + 6′-membered: O1C2NN1C3O2 88.2° (O1–Pt–N1) and 92.0° (N1–Pt–O2).
In Pt(η3N1N2X1) (PL) derivatives are
5 + 5-membered: N1C2N2C2C1 78.2° (N1–Pt–N2) and 80.7° (N2–Pt–C1);
5 + 5′-membered: N1C2N2NCS1 78.8° (N1–Pt–N2) and 82.8° (N2–Pt–S1);
5 + 5-membered: N1CNN2NCSe1 78.7° (N1–Pt–N2) and 82.3° (N2–Pt–Se1).

There are at least two contributing factors to the size of chelate bond angles, both ligands based. One is steric constraints imposed on the ligand, and the other is the need to accommodate denticity appropriately.

In transition metal complexes, the oxidation state plays a leading role in the geometry formed, and platinum is no exception. In four coordinates, Pt(ii) prefers a square-planar geometry. The utility of a simple metric to assess molecule shape and degree of distortion as well as exemplified best the τ4 parameter for a square-planar geometry by an equation introduced by Yang et al. [26]:

τ 4 = 360 ( α + β ) 141 F .

The values of τ4 range from 0.00 for a perfect square-planar geometry to 1.00 for a perfect tetrahedral geometry since 360 − 2(109.5) = 141.

It is well known that the trans L–Pt–L bond angles and the number and type of atoms involved in respective rings are responsible for a distortion of the square-planar geometry about the Pt(ii) atom. The total mean values of trans-α-L–Pt–L (L are terminal atoms of the respective η3-ligand) bond angles, and trans-β-N′–Pt–P (N′ central atom N1 or N2 of the rings) bond angles and τ 4 are given in Table 3.

Table 3

Mean values of trans-α-L–Pt–L and trans-β-N’–Pt–P as well as τ4

Metallocyclic rings α-L–Pt–L (°) β–N′–Pt–P (°) τ 4
5 + 5 membered
N1C2N2C2C1 157.5 177.3 0.179
C1C2N1C2C2 158.8 171.6 0.210
N1CNN2NCS1 151.6 171.8 0.259
N1CNN2NCSe1 162.0 176.2 0.154
N1C2N2NCS1 162.2 177.1 0.147
5 + 6 membered
Se1C2N1NC2Se2 176.2 170.9 0.091
O1C2N1C3O2 176.4 172.2 0.081
6 + 6 membered
O1C2NN1C3O2 170.5 175.0 0.103
O1C3N1C3O2 176.0 177.0 0.048

There is a cooperative effect between a degree of distortion of square-planar geometry about Pt(ii) atom and the trans-L–Pt–L angles. The degree of distortion grows (τ4) when trans-L–Pt–L angles diminish. There is also a cooperative effect between a degree of distortion and trans-influence of X atom/ligand when trans-influence of the respective X weakness degree of distortion increases.

The covalent radii of the donor atoms and their sums in evaluated structures are responsible for the main structural characteristics (L–Pt–L angles, bond lengths of donor and acceptor atoms) and, by that, distortion (τ4) of the complexes. These structural characteristics and distortion, evaluated and calculated in our study, as well as resulting structural trends, discussed therein, will be reflected in the physical–chemical properties of the complexes (e.g., catalytic activity being relevant for the synthesis and catalysis studies).

Acknowledgements

This work was supported by the Faculty of Pharmacy, Comenius University Bratislava. Structural data used in this study for discussion and calculations were obtained from the Cambridge Crystallographic Database (CCDB) with an institutional license of the Slovak University of Technology in Bratislava.

  1. Funding information: This work was supported by the projects VEGA 1/0514/22 and VEGA 1/0146/23.

  2. Author contributions: Conceptualization, M.M. and P.M.; methodology M.M. and P.M.; writing – original draft preparation, M.M., P.M., V.M., and D.Ž.; data curation, M.M.; writing – review and editing, M.M., P.M., V.M., and D.Ž.; supervision, M.M. and P.M.; funding acquisition, P.M. The authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  3. Conflict of interest: The authors declare no conflict of interest.

  4. Ethical approval: The conducted research is not related to either human or animal use.

  5. Data availability statement: All data generated or analyzed during this study are included in this published article.

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Received: 2023-09-06
Revised: 2024-01-22
Accepted: 2024-02-06
Published Online: 2024-03-22

© 2024 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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  6. Sonochemical synthesis of gold nanoparticles mediated by potato starch: Its performance in the treatment of esophageal cancer
  7. Computational study of ADME-Tox prediction of selected phytochemicals from Punica granatum peels
  8. Phytochemical analysis, in vitro antioxidant and antifungal activities of extracts and essential oil derived from Artemisia herba-alba Asso
  9. Two triazole-based coordination polymers: Synthesis and crystal structure characterization
  10. Phytochemical and physicochemical studies of different apple varieties grown in Morocco
  11. Synthesis of multi-template molecularly imprinted polymers (MT-MIPs) for isolating ethyl para-methoxycinnamate and ethyl cinnamate from Kaempferia galanga L., extract with methacrylic acid as functional monomer
  12. Nutraceutical potential of Mesembryanthemum forsskaolii Hochst. ex Bioss.: Insights into its nutritional composition, phytochemical contents, and antioxidant activity
  13. Evaluation of influence of Butea monosperma floral extract on inflammatory biomarkers
  14. Cannabis sativa L. essential oil: Chemical composition, anti-oxidant, anti-microbial properties, and acute toxicity: In vitro, in vivo, and in silico study
  15. The effect of gamma radiation on 5-hydroxymethylfurfural conversion in water and dimethyl sulfoxide
  16. Hollow mushroom nanomaterials for potentiometric sensing of Pb2+ ions in water via the intercalation of iodide ions into the polypyrrole matrix
  17. Determination of essential oil and chemical composition of St. John’s Wort
  18. Computational design and in vitro assay of lantadene-based novel inhibitors of NS3 protease of dengue virus
  19. Anti-parasitic activity and computational studies on a novel labdane diterpene from the roots of Vachellia nilotica
  20. Microbial dynamics and dehydrogenase activity in tomato (Lycopersicon esculentum Mill.) rhizospheres: Impacts on growth and soil health across different soil types
  21. Correlation between in vitro anti-urease activity and in silico molecular modeling approach of novel imidazopyridine–oxadiazole hybrids derivatives
  22. Spatial mapping of indoor air quality in a light metro system using the geographic information system method
  23. Iron indices and hemogram in renal anemia and the improvement with Tribulus terrestris green-formulated silver nanoparticles applied on rat model
  24. Integrated track of nano-informatics coupling with the enrichment concept in developing a novel nanoparticle targeting ERK protein in Naegleria fowleri
  25. Cytotoxic and phytochemical screening of Solanum lycopersicum–Daucus carota hydro-ethanolic extract and in silico evaluation of its lycopene content as anticancer agent
  26. Protective activities of silver nanoparticles containing Panax japonicus on apoptotic, inflammatory, and oxidative alterations in isoproterenol-induced cardiotoxicity
  27. pH-based colorimetric detection of monofunctional aldehydes in liquid and gas phases
  28. Investigating the effect of resveratrol on apoptosis and regulation of gene expression of Caco-2 cells: Unravelling potential implications for colorectal cancer treatment
  29. Metformin inhibits knee osteoarthritis induced by type 2 diabetes mellitus in rats: S100A8/9 and S100A12 as players and therapeutic targets
  30. Effect of silver nanoparticles formulated by Silybum marianum on menopausal urinary incontinence in ovariectomized rats
  31. Synthesis of new analogs of N-substituted(benzoylamino)-1,2,3,6-tetrahydropyridines
  32. Response of yield and quality of Japonica rice to different gradients of moisture deficit at grain-filling stage in cold regions
  33. Preparation of an inclusion complex of nickel-based β-cyclodextrin: Characterization and accelerating the osteoarthritis articular cartilage repair
  34. Empagliflozin-loaded nanomicelles responsive to reactive oxygen species for renal ischemia/reperfusion injury protection
  35. Preparation and pharmacodynamic evaluation of sodium aescinate solid lipid nanoparticles
  36. Assessment of potentially toxic elements and health risks of agricultural soil in Southwest Riyadh, Saudi Arabia
  37. Theoretical investigation of hydrogen-rich fuel production through ammonia decomposition
  38. Biosynthesis and screening of cobalt nanoparticles using citrus species for antimicrobial activity
  39. Investigating the interplay of genetic variations, MCP-1 polymorphism, and docking with phytochemical inhibitors for combatting dengue virus pathogenicity through in silico analysis
  40. Ultrasound induced biosynthesis of silver nanoparticles embedded into chitosan polymers: Investigation of its anti-cutaneous squamous cell carcinoma effects
  41. Copper oxide nanoparticles-mediated Heliotropium bacciferum leaf extract: Antifungal activity and molecular docking assays against strawberry pathogens
  42. Sprouted wheat flour for improving physical, chemical, rheological, microbial load, and quality properties of fino bread
  43. Comparative toxicity assessment of fisetin-aided artificial intelligence-assisted drug design targeting epibulbar dermoid through phytochemicals
  44. Acute toxicity and anti-inflammatory activity of bis-thiourea derivatives
  45. Anti-diabetic activity-guided isolation of α-amylase and α-glucosidase inhibitory terpenes from Capsella bursa-pastoris Linn.
  46. GC–MS analysis of Lactobacillus plantarum YW11 metabolites and its computational analysis on familial pulmonary fibrosis hub genes
  47. Green formulation of copper nanoparticles by Pistacia khinjuk leaf aqueous extract: Introducing a novel chemotherapeutic drug for the treatment of prostate cancer
  48. Improved photocatalytic properties of WO3 nanoparticles for Malachite green dye degradation under visible light irradiation: An effect of La doping
  49. One-pot synthesis of a network of Mn2O3–MnO2–poly(m-methylaniline) composite nanorods on a polypyrrole film presents a promising and efficient optoelectronic and solar cell device
  50. Groundwater quality and health risk assessment of nitrate and fluoride in Al Qaseem area, Saudi Arabia
  51. A comparative study of the antifungal efficacy and phytochemical composition of date palm leaflet extracts
  52. Processing of alcohol pomelo beverage (Citrus grandis (L.) Osbeck) using saccharomyces yeast: Optimization, physicochemical quality, and sensory characteristics
  53. Specialized compounds of four Cameroonian spices: Isolation, characterization, and in silico evaluation as prospective SARS-CoV-2 inhibitors
  54. Identification of a novel drug target in Porphyromonas gingivalis by a computational genome analysis approach
  55. Physico-chemical properties and durability of a fly-ash-based geopolymer
  56. FMS-like tyrosine kinase 3 inhibitory potentials of some phytochemicals from anti-leukemic plants using computational chemical methodologies
  57. Wild Thymus zygis L. ssp. gracilis and Eucalyptus camaldulensis Dehnh.: Chemical composition, antioxidant and antibacterial activities of essential oils
  58. 3D-QSAR, molecular docking, ADMET, simulation dynamic, and retrosynthesis studies on new styrylquinolines derivatives against breast cancer
  59. Deciphering the influenza neuraminidase inhibitory potential of naturally occurring biflavonoids: An in silico approach
  60. Determination of heavy elements in agricultural regions, Saudi Arabia
  61. Synthesis and characterization of antioxidant-enriched Moringa oil-based edible oleogel
  62. Ameliorative effects of thistle and thyme honeys on cyclophosphamide-induced toxicity in mice
  63. Study of phytochemical compound and antipyretic activity of Chenopodium ambrosioides L. fractions
  64. Investigating the adsorption mechanism of zinc chloride-modified porous carbon for sulfadiazine removal from water
  65. Performance repair of building materials using alumina and silica composite nanomaterials with electrodynamic properties
  66. Effects of nanoparticles on the activity and resistance genes of anaerobic digestion enzymes in livestock and poultry manure containing the antibiotic tetracycline
  67. Effect of copper nanoparticles green-synthesized using Ocimum basilicum against Pseudomonas aeruginosa in mice lung infection model
  68. Cardioprotective effects of nanoparticles green formulated by Spinacia oleracea extract on isoproterenol-induced myocardial infarction in mice by the determination of PPAR-γ/NF-κB pathway
  69. Anti-OTC antibody-conjugated fluorescent magnetic/silica and fluorescent hybrid silica nanoparticles for oxytetracycline detection
  70. Curcumin conjugated zinc nanoparticles for the treatment of myocardial infarction
  71. Identification and in silico screening of natural phloroglucinols as potential PI3Kα inhibitors: A computational approach for drug discovery
  72. Exploring the phytochemical profile and antioxidant evaluation: Molecular docking and ADMET analysis of main compounds from three Solanum species in Saudi Arabia
  73. Unveiling the molecular composition and biological properties of essential oil derived from the leaves of wild Mentha aquatica L.: A comprehensive in vitro and in silico exploration
  74. Analysis of bioactive compounds present in Boerhavia elegans seeds by GC-MS
  75. Homology modeling and molecular docking study of corticotrophin-releasing hormone: An approach to treat stress-related diseases
  76. LncRNA MIR17HG alleviates heart failure via targeting MIR17HG/miR-153-3p/SIRT1 axis in in vitro model
  77. Development and validation of a stability indicating UPLC-DAD method coupled with MS-TQD for ramipril and thymoquinone in bioactive SNEDDS with in silico toxicity analysis of ramipril degradation products
  78. Biosynthesis of Ag/Cu nanocomposite mediated by Curcuma longa: Evaluation of its antibacterial properties against oral pathogens
  79. Development of AMBER-compliant transferable force field parameters for polytetrafluoroethylene
  80. Treatment of gestational diabetes by Acroptilon repens leaf aqueous extract green-formulated iron nanoparticles in rats
  81. Development and characterization of new ecological adsorbents based on cardoon wastes: Application to brilliant green adsorption
  82. A fast, sensitive, greener, and stability-indicating HPLC method for the standardization and quantitative determination of chlorhexidine acetate in commercial products
  83. Assessment of Se, As, Cd, Cr, Hg, and Pb content status in Ankang tea plantations of China
  84. Effect of transition metal chloride (ZnCl2) on low-temperature pyrolysis of high ash bituminous coal
  85. Evaluating polyphenol and ascorbic acid contents, tannin removal ability, and physical properties during hydrolysis and convective hot-air drying of cashew apple powder
  86. Development and characterization of functional low-fat frozen dairy dessert enhanced with dried lemongrass powder
  87. Scrutinizing the effect of additive and synergistic antibiotics against carbapenem-resistant Pseudomonas aeruginosa
  88. Preparation, characterization, and determination of the therapeutic effects of copper nanoparticles green-formulated by Pistacia atlantica in diabetes-induced cardiac dysfunction in rat
  89. Antioxidant and antidiabetic potentials of methoxy-substituted Schiff bases using in vitro, in vivo, and molecular simulation approaches
  90. Anti-melanoma cancer activity and chemical profile of the essential oil of Seseli yunnanense Franch
  91. Molecular docking analysis of subtilisin-like alkaline serine protease (SLASP) and laccase with natural biopolymers
  92. Overcoming methicillin resistance by methicillin-resistant Staphylococcus aureus: Computational evaluation of napthyridine and oxadiazoles compounds for potential dual inhibition of PBP-2a and FemA proteins
  93. Exploring novel antitubercular agents: Innovative design of 2,3-diaryl-quinoxalines targeting DprE1 for effective tuberculosis treatment
  94. Drimia maritima flowers as a source of biologically potent components: Optimization of bioactive compound extractions, isolation, UPLC–ESI–MS/MS, and pharmacological properties
  95. Estimating molecular properties, drug-likeness, cardiotoxic risk, liability profile, and molecular docking study to characterize binding process of key phyto-compounds against serotonin 5-HT2A receptor
  96. Fabrication of β-cyclodextrin-based microgels for enhancing solubility of Terbinafine: An in-vitro and in-vivo toxicological evaluation
  97. Phyto-mediated synthesis of ZnO nanoparticles and their sunlight-driven photocatalytic degradation of cationic and anionic dyes
  98. Monosodium glutamate induces hypothalamic–pituitary–adrenal axis hyperactivation, glucocorticoid receptors down-regulation, and systemic inflammatory response in young male rats: Impact on miR-155 and miR-218
  99. Quality control analyses of selected honey samples from Serbia based on their mineral and flavonoid profiles, and the invertase activity
  100. Eco-friendly synthesis of silver nanoparticles using Phyllanthus niruri leaf extract: Assessment of antimicrobial activity, effectiveness on tropical neglected mosquito vector control, and biocompatibility using a fibroblast cell line model
  101. Green synthesis of silver nanoparticles containing Cichorium intybus to treat the sepsis-induced DNA damage in the liver of Wistar albino rats
  102. Quality changes of durian pulp (Durio ziberhinus Murr.) in cold storage
  103. Study on recrystallization process of nitroguanidine by directly adding cold water to control temperature
  104. Determination of heavy metals and health risk assessment in drinking water in Bukayriyah City, Saudi Arabia
  105. Larvicidal properties of essential oils of three Artemisia species against the chemically insecticide-resistant Nile fever vector Culex pipiens (L.) (Diptera: Culicidae): In vitro and in silico studies
  106. Design, synthesis, characterization, and theoretical calculations, along with in silico and in vitro antimicrobial proprieties of new isoxazole-amide conjugates
  107. The impact of drying and extraction methods on total lipid, fatty acid profile, and cytotoxicity of Tenebrio molitor larvae
  108. A zinc oxide–tin oxide–nerolidol hybrid nanomaterial: Efficacy against esophageal squamous cell carcinoma
  109. Research on technological process for production of muskmelon juice (Cucumis melo L.)
  110. Physicochemical components, antioxidant activity, and predictive models for quality of soursop tea (Annona muricata L.) during heat pump drying
  111. Characterization and application of Fe1−xCoxFe2O4 nanoparticles in Direct Red 79 adsorption
  112. Torilis arvensis ethanolic extract: Phytochemical analysis, antifungal efficacy, and cytotoxicity properties
  113. Magnetite–poly-1H pyrrole dendritic nanocomposite seeded on poly-1H pyrrole: A promising photocathode for green hydrogen generation from sanitation water without using external sacrificing agent
  114. HPLC and GC–MS analyses of phytochemical compounds in Haloxylon salicornicum extract: Antibacterial and antifungal activity assessment of phytopathogens
  115. Efficient and stable to coking catalysts of ethanol steam reforming comprised of Ni + Ru loaded on MgAl2O4 + LnFe0.7Ni0.3O3 (Ln = La, Pr) nanocomposites prepared via cost-effective procedure with Pluronic P123 copolymer
  116. Nitrogen and boron co-doped carbon dots probe for selectively detecting Hg2+ in water samples and the detection mechanism
  117. Heavy metals in road dust from typical old industrial areas of Wuhan: Seasonal distribution and bioaccessibility-based health risk assessment
  118. Phytochemical profiling and bioactivity evaluation of CBD- and THC-enriched Cannabis sativa extracts: In vitro and in silico investigation of antioxidant and anti-inflammatory effects
  119. Investigating dye adsorption: The role of surface-modified montmorillonite nanoclay in kinetics, isotherms, and thermodynamics
  120. Antimicrobial activity, induction of ROS generation in HepG2 liver cancer cells, and chemical composition of Pterospermum heterophyllum
  121. Study on the performance of nanoparticle-modified PVDF membrane in delaying membrane aging
  122. Impact of cholesterol in encapsulated vitamin E acetate within cocoliposomes
  123. Review Articles
  124. Structural aspects of Pt(η3-X1N1X2)(PL) (X1,2 = O, C, or Se) and Pt(η3-N1N2X1)(PL) (X1 = C, S, or Se) derivatives
  125. Biosurfactants in biocorrosion and corrosion mitigation of metals: An overview
  126. Stimulus-responsive MOF–hydrogel composites: Classification, preparation, characterization, and their advancement in medical treatments
  127. Electrochemical dissolution of titanium under alternating current polarization to obtain its dioxide
  128. Special Issue on Recent Trends in Green Chemistry
  129. Phytochemical screening and antioxidant activity of Vitex agnus-castus L.
  130. Phytochemical study, antioxidant activity, and dermoprotective activity of Chenopodium ambrosioides (L.)
  131. Exploitation of mangliculous marine fungi, Amarenographium solium, for the green synthesis of silver nanoparticles and their activity against multiple drug-resistant bacteria
  132. Study of the phytotoxicity of margines on Pistia stratiotes L.
  133. Special Issue on Advanced Nanomaterials for Energy, Environmental and Biological Applications - Part III
  134. Impact of biogenic zinc oxide nanoparticles on growth, development, and antioxidant system of high protein content crop (Lablab purpureus L.) sweet
  135. Green synthesis, characterization, and application of iron and molybdenum nanoparticles and their composites for enhancing the growth of Solanum lycopersicum
  136. Green synthesis of silver nanoparticles from Olea europaea L. extracted polysaccharides, characterization, and its assessment as an antimicrobial agent against multiple pathogenic microbes
  137. Photocatalytic treatment of organic dyes using metal oxides and nanocomposites: A quantitative study
  138. Antifungal, antioxidant, and photocatalytic activities of greenly synthesized iron oxide nanoparticles
  139. Special Issue on Phytochemical and Pharmacological Scrutinization of Medicinal Plants
  140. Hepatoprotective effects of safranal on acetaminophen-induced hepatotoxicity in rats
  141. Chemical composition and biological properties of Thymus capitatus plants from Algerian high plains: A comparative and analytical study
  142. Chemical composition and bioactivities of the methanol root extracts of Saussurea costus
  143. In vivo protective effects of vitamin C against cyto-genotoxicity induced by Dysphania ambrosioides aqueous extract
  144. Insights about the deleterious impact of a carbamate pesticide on some metabolic immune and antioxidant functions and a focus on the protective ability of a Saharan shrub and its anti-edematous property
  145. A comprehensive review uncovering the anticancerous potential of genkwanin (plant-derived compound) in several human carcinomas
  146. A study to investigate the anticancer potential of carvacrol via targeting Notch signaling in breast cancer
  147. Assessment of anti-diabetic properties of Ziziphus oenopolia (L.) wild edible fruit extract: In vitro and in silico investigations through molecular docking analysis
  148. Optimization of polyphenol extraction, phenolic profile by LC-ESI-MS/MS, antioxidant, anti-enzymatic, and cytotoxic activities of Physalis acutifolia
  149. Phytochemical screening, antioxidant properties, and photo-protective activities of Salvia balansae de Noé ex Coss
  150. Antihyperglycemic, antiglycation, anti-hypercholesteremic, and toxicity evaluation with gas chromatography mass spectrometry profiling for Aloe armatissima leaves
  151. Phyto-fabrication and characterization of gold nanoparticles by using Timur (Zanthoxylum armatum DC) and their effect on wound healing
  152. Does Erodium trifolium (Cav.) Guitt exhibit medicinal properties? Response elements from phytochemical profiling, enzyme-inhibiting, and antioxidant and antimicrobial activities
  153. Integrative in silico evaluation of the antiviral potential of terpenoids and its metal complexes derived from Homalomena aromatica based on main protease of SARS-CoV-2
  154. 6-Methoxyflavone improves anxiety, depression, and memory by increasing monoamines in mice brain: HPLC analysis and in silico studies
  155. Simultaneous extraction and quantification of hydrophilic and lipophilic antioxidants in Solanum lycopersicum L. varieties marketed in Saudi Arabia
  156. Biological evaluation of CH3OH and C2H5OH of Berberis vulgaris for in vivo antileishmanial potential against Leishmania tropica in murine models
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