Home Organodiphosphines in Pt{η2-P(X)nP}(Cl)2 (n = 4, 5, 6, 7, 8, 10, 11, 15, 18) derivates: Structural aspects
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Organodiphosphines in Pt{η2-P(X)nP}(Cl)2 (n = 4, 5, 6, 7, 8, 10, 11, 15, 18) derivates: Structural aspects

  • Melník Milan EMAIL logo , Veronika Mikušová and Peter Mikuš EMAIL logo
Published/Copyright: July 11, 2024
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Main Group Metal Chemistry
From the journal Main Group Metal Chemistry Volume 47 Issue 1

Abstract

This structural study includes over 70 Pt{η2-P(X) n P}(Cl)2 (n = 4, 5, 6, 7, 8, 10, 11, 15, 18) derivates in which organodiphosphines create wide varieties of the metallocyclic rings: 7 membered (PC4P (most common), POC2OP, PNC2NP, PSC2SP, PNC2OP; 8 membered (PC5P, PC2OC2P, PC2NC2P); 9 membered (PC6P, POC4OP); 10 membered (POC5OP, PC2OCOC2P; PC3OC3P); 11 membered (PC8P,PNC6NP,POC6OP), 13 membered (PC3NC2NC3P); 14 membered (P(C2Cl3C2P); 18 membered (PC4NC2NC2NC4P); and 21 membered (POC2NC10NC2OP). These complexes crystallized in three crystal classes: triclinic (15 examples) < orthorhombic (17 examples) < monoclinic (39 examples). In these complexes, the most common is a predominantly cis arrangement (68 examples) and only 3 examples with trans configuration. The total mean values of Pt–L bond distances in the complexes (cis vs trans configuration) are 2.232 Å (L = P), 2.353 Å (L = Cl) vs 2.312 and 2.307 Å, respectively. The structural data are compared and discussed with those found in cis-Pt(η2-P(X) n P)(Cl)2 (n = 1, 2, 3) in which organodiphosphines form four-PCP, PNP; five-PC-CP; PC═CP; six-PC3P, PNCNP, PCCOP, PCCNP, PCSCP, PCSiCP; membered metallocyclic rings. Some complexes are examples of distortion and cis–trans isomerism.

Keywords: structure; Pt(η2-P(X) n P)(Cl)2 (n = 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 15, 18); organodiphosphines; isomers

Abbreviations

bnbp

1,1′-binaphthyl-2,2′-diyl-diphosphite

Bu2P(C8H8)PPh2

dibutyl(2-diphenylphosphino)methyl(benzyl)phosphine

(η2-C4H10N2)P{N(Me)(CH2CH2)N(Me)}P(η2-C4H10N2)}

bis{(N,N′-dimethylamino ethane) phosphine}-1,2-diaminetriethylamine

(η2-C5H10O2P{OCH(COOMe)CH(COOMe)O}P(η2-C5H10O2)

(dimethyl-2,3-bis(5,5-dimethyl-1,3,2-dioxaphosphinan-2-yl) oxy)succinate

(η2-C10H18)P(C8H8)P(η2-C10H18)

2,2′-(1,2-phenylenebis(methylene)bis(5,5,6-trimethyl-2phosphabicyclo[2.2.2]octane

(η2-C12H18O2)P(NC5H9O)P(η2-C12H18O2)

N-(2,2′-biphenoxyphosphino)-2-(2,2′biphenoxyphosphinolymethyl)pyrrolidine

(η2-C17H16NO2)P{OCH(Ph)CH(Ph)O}P(η2-C17H16NO2)

1,2-diphenyl-1,2-bis(5,6-dimethyl-N-phenyl-7-phospha-5-norbomene-2,3-dicarboximide-7-oxy)ethyl

Et2NP(η2-N2)C9H9O)2PNEt2

bis(1,2-bis(2-(diethylamino)-1-methyl-4-oxobenzeno(e)-1,3,2λ3diazaphosphozinan-2-yl)ethane

Ph2P(NC5H9O)PPh2

(1-(diphenylphosphino)-2-(dipgenylphosphino)oxy)methyl) pyrrolidine

Ph2P(C9H12)PPh2

bicyclo[2.2.1]hept-5-ene-2,3-diylbismethylene)bis (diphenylphosphine)

Ph2P(C32H20)PPh2

15,15′-bi(16-diphenylphosphino)tetracyclo(6.6.2.02,7 09,14)hexadeca-2(7),3,5,9(14),10,12,15-heptenyl

Ph2P(C24H20)PPh2

2,2′-bis(diphenylphosphino)-1,1′-binaphthoyl

Ph2P(C12H8)PPh2

2,2′-bis(diphenylphosphino)-1,1′-biphenyl

Ph2P{OCH(Ph)CH(Ph)O}PPh2

1,2-bis(diphenylphosphinooxy)-1,2-diphenylethane

Ph2P{SC(COOMe)C(COOMe)S}PPh2

meso-dimethyl-2,3-bis(diphenylphosphinothio (succinate)

Ph2P(C12H12S2)PPh2

2,2′-5,5′-tetramethyl-4,4′-bis(diphenylphosphino)-3,3′-bithiophene

Ph2P(CH2C7H8O2CH2)PPh2

2,2-dimethyl-4,5-bis(diphenylhosphinomethyl)-1,3-dioxalane

Ph2P(C20H18)PPh2

1,2-bis(α-(diphenylphosphino)benzylidine)cyclohexane

Ph2P{OCC(Et)O}PPh2

1,2-bis(diphenylphosphito)butane

Ph2P{OCH(Ph))CH2O}PPh2

1,2-bis(diphenylphosphinooxy)ethylbenzene

Ph2P(C6H10O2)PPh2

1,2-bis(diphenylphosphinooxy)cyclohexane

Ph2P(C24H14)PPh2

1,16-bis(diphenylphosphino)tetraphenylene

Ph2P(C18H22N2)PPh2

6,6′-bis(diphenylphosphino-N,N,N′,N′,4,4′-hexa methylbiphenyl-2,2′diamine

Ph2P(C20H20N2)PPh2

3,3′-bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphtalene

Pri 2P{N(CH2Ph)CH2CH2N(CH2Ph)}PPri 2

N,N′-dibenzyl-N,N′-bis(diizopropyl phosphino)-1,2ethylendiamine

(C9H11O)2P(OC20H12O)P(OC9H11)2

2,2′-bis(bis(2-isopropylphenoxy)(phosphineoxy)-1,1′binaphthalene

(η2-C10H16O3)P(OC8H8O)P(η2-C10H16O3)

8,8′-(1,2-phenylenebis(methyleneoxy)bis(1,3,5,7-tetramethyl-2,4,6-trioxa-8-phosphatricyclo[3.3.1.13,7]decane

(η2-C16H12)P(C15H12)P(η2-C16H12)

9,9-dimethyl-4,5-bis(2,5-diphenylphospholyl)-xanthene

(η2-C20H12O2)P(C15H12O)P(η2-C20H12O2)

4,5-bis(dinaphtho[2,1-d:1′,2′-f][1,3,2]-dioxaphosphin)-9,9-dimethylxantene

(η2-C22H28O3)P(C15H12O)P(η2-C22H28O3)

4,5-bis(3-terc-butyl-5-methoxy-1,1′-biphenyl-2,2′-dioxy)phosphino-9,9-dimethylxantene

(η2-C8H12)P(C14H16)P(η2-C8H12)

2,2′-bis((9-phosphabicyclo[3.3.1]nonan-9-yl)-methyl)1,1′-biphenyl

Ph2P(C18H12)PPh2

1,2-bis(2-(diphenylphosphino)phenyl)benzene

Ph2P(C13H8O)PPh2

2,2′-bis(diphenylphosphino)benzophenone

Ph2P(C14H12OSi)PPh2

4,6-bis(diphenylphosphino)-10,10-dimethyl-10H-phenoxasilin

Ph2P(C16H12O)PPh2

bis(diphenylphosphino)-9,9-dimethyl-9H-xanthene-4,5-diyl

Ph2P(C16H14)PPh2 bis(diphenylphosphane)

tricyclo[8.2.2.24]hexadeca-1(12)-4,6,10,13,15-hexane-5,12-diyl-Ph2P(C20H12)PPh2 1,8-bis(diphenylphosphino)triptycene

Ph2P(C20H16O2)PPh2

1,2-bis(3-(diphenylphosphino)-4-methoxyphenyl)benzene

Ph2P(C23H26O2)PPh2

8,8′-bis(diphenylphosphido)-4,4,4′,4′,6,6′-hexamethylspiro-2,2′bichroman

Ph2P(C6H8O3)PPh2

3,6-bis(diphenylphosphinooxy)-hexahydrofuro-(3,2-b)furan

Ph2P(C7H6OC7H6)PPh2

((oxy(bis)methylene-2,1-phenylene))bis(diphenyl-phosphine)

Ph2P(CH2)5PPh2

1,5-bis(diphenylphosphino)pentane

Ph2P(NC12H8N)PPh2

5,10-bis(diphenylphosphino)phenozine

Ph2P(OC7H10O)PPh2

(3-endo-6-endo-bis(diphenylphosphinooxy)bicyclo[3.2.0]-heptane)

Ph2P{(CH2)2N(P)(CH2)2P}PPh2

N,N-bis(2-(diphenylphosphino)ethyl)aniline

Ph2P{C10H6(CH2)C10H6O}PPh2

1,1′-methylene-bis(2-((diphenylphosphino)oxy)naphthalene

Ph2P{OC6H4(CH2)C6H4O}PPh2

methylene-di-2,1-phenylenebis(diphenyl phosphinate)

Pri 2P(C18H24)PPri 2

([11,21:22,31-terphenyl]-12,32-diyl)-[bis(bis(propan-2-yl)-phosphane]

Pri 2P(C20H12)PPri 2

1,8-bis(diisopropylphosphino)triptycene

Pri 2P(OC12H8O)PPri 2

2,2′-bis(diisopropylphosphinito)-1,1′-biphenyl

Pri 2P(OC14H12O)PPri 2

2,2′-bis(diisopropylphosphanyloxymethyl)-1,1′-biphenyl

Pri 2P(OC6H10O)PPri 2

1,3-bis(diisopropylphosphonite)cyclohexane Pri 2P{OC12H8(CH2)O}PPri 2 (2-diisopropylphosphanyloxy-2′-diisopropylphosphanyloxymethyl-1,1′-biphenyl

Ph2P(C22H28N2O2)PPh2

1,6-bis(2-diphenylphosphonoxymethyl-1-azabryclo [2.2.2] octan5-yl) hix-3-en-1,5-diyne

Ph2P(C22H25N3)PPh2

N,N-bis(2-((3-diphenylphosphino)benzyl)amino)phenyl)-N-metylamine

Ph2P(C8H16O3)PPh2

1,11-bis(diphenylphosphino)-3,6,9-trioxan-decane

1 Introduction

Phosphorous donor chiral ligands are very attractive and useful forming wide variability of stereochemistry about central transition metals and platinum is no exception. It should not be overlooked that platinum has played a crucial role in the development of many branches of science, even though the amount used has been small reliable platinum crucibles were vital in classical analysis which laid the foundation of modern chemistry. The chemistry of platinum is an important area, particularly in the fields of biochemistry, catalysis, and theory.

Organophosphines are very attractive and useful ligands forming a wide variability of stereo chemistry about central traction metals and Pt is no exception. Over 2,500 platinum complexes have been reviewed [1]. Recently, we analyzed structural formulas of organomonophosphines in monomeric PtP2Cl2 derivates [2].

Recently, we also analyzed the structural parameter of monomeric Pt{η2-P(X) n P}Cl2 (n = 1, 2, 3), in which P,P-donor ligands are organodiphosphines create four-, five-, and six-membered metallocyclic rings [3].

This structural study aims to classify and analyze structural parameters of Pt{η2-P(X) n P)Cl2 (n = 4, 5, 6, 7, 8, 10, 11, 15, 18), in which organodiphosphines create 7, 8, 9, 10, 11, 13, 14, 18, and 21 metallocyclic rings. These data are discussed with four-, five-, and six-membered metallocycles [3].

2 cis-Pt{η2-P(x)4P}Cl2 derivatives

There are over 30 monomeric Pt(ii) complexes with such inner coordination spheres in which organodiphosphines form seven-membered metallocyclic rings. These metallocycles can be divided into five subgroups: PC4P, POC2OP, PNC2NP, PSC2SP, and PNC2OP.

2.1 Pt(η2-PC4P)Cl2 type

This type with 17 examples is the most common. These complexes crystallized in the three crystal classes: triclinic (three examples), orthorhombic (seven examples), and monoclinic (seven examples). Pale yellow [Pt{η2-Ph2P(CH2C7H8O2CH2)PPh2}(Cl)2] exists in two crystal classes: triclinic [4] and orthorhombic [5]. The triclinic complex even contains two crystallographically independent molecules within the same crystal. In each complex, the organodiphosphine forms a seven-membered metallocyclic ring with the values of 97° (molecule 1), 96° (molecule 2), and 97.6° (orthorhombic). The Pt(ii) atoms have a distorted square-planar environment (PtP2Cl2). The mean Pt–L bond distances are 2.33 Å (L = Cl) and 2.255 Å (P) (molecule 1), 2.35 and 2.25 Å (molecule 2), and 2.324 and 2.246 Å (orthorhombic). The sum of all four Pt–L bond distances growing in the order: 9.13 Å (orthorhombic) < 9.17 Å (molecule 1) < 9.20 Å (molecule 2); this indicates that the inner coordination sphere is less crowded in the given order. These complexes are classical examples of distortion isomerism [6].

In the following 15 complexes, namely [Pt{η2-Ph2P(CH2CH2CH2CH2)PPh2}(Cl)2] [7], [Pt{η2-Ph2P(C9H12)PPh2}(Cl)2]CH2Cl2 (at 233 K) [8], [Pt{η2-Ph2P(C20H18)PPh2}(Cl)2]·4CHCl3 (at 153 K) [9], [Pt{η2-Bu2P(C8H8)PPh2}(Cl)2]·CH2Cl2 (at 100 K) [10], [Pt{η2But 2P(C8H8)PPh2}(Cl)2]·CH2Cl2 (at 100 K) [10], [Pt{η2-But 2P(C8H8)PBut 2}(Cl)2]·CHCl3 (at 120 K) [11], [Pt{η2Ph2P(C32H20)PPh2}(Cl)2]·2CH2Cl2 (at 150 K) [12], [Pt{η2Ph2P(C12H18)PPh2}(Cl)2]·0.5CH2Cl2 [13], [Pt{η2Ph2P(C24H20)PPh2}(Cl)2] (at 150 K) [14], [Pt{η2-Ph2P(C12H8)PPh2}(Cl)2]·CH2Cl2 [15], [Pt{η2Ph2P(C24H14)PPh2}(Cl)2]·2CH2Cl2 [16], [Pt{η2Ph2P(C20H20N2)PPh2}(Cl)2]·4CH2Cl2 (at 150 K) [17], [Pt{η2Ph2P(C18H22N2)PPh2}(Cl)2]·2CH2Cl2 (at 100 K) [18], [Pt{η2-Ph2P(C12H12S2)PPh2}(Cl)2] [19], and [Pt{η2-(η2-C10H18)P(C8H8)P(η2C10H18)}(Cl)2]·CH3CN (at 150 K) [20], each homobidentate-P,P′ donor ligand creates seven-membered metallocyclic rings of the PC4P type. The structure of monoclinic [Pt{η2-Ph2P(C18H22N2)PPh2}(Cl)2] [18] is shown in Figure 1 as an example. The mean values of Pt–L bond distances are 2.250 Å (L = P) and 2.335 Å (Cl). The mean values of cis-L–Pt–L bond angles open in the order: 86.8° (Cl–Pt–Cl) < 88.2° (Cl-PtP) < 96.7° (P-Pt-P). The mean value of trans-Cl-Pt-P bond angles is 173.2°.

Figure 1 Structure of [Pt{η2-Ph2P(C18H22N2)PPh2}(Cl)2] [18].
Figure 1

Structure of [Pt{η2-Ph2P(C18H22N2)PPh2}(Cl)2] [18].

2.2 Pt(η2-POC2OP)Cl2 type

There are six examples of this type. These complexes crystallized in the three crystal classes: orthorhombic (one example), triclinic (one example), and monoclinic (four examples). Such complexes are [Pt{η2-Ph2P{OCC(Et)O}PPh2}(Cl)2] [21], [Pt{η2Ph2P(OCH(Ph)CH(Ph)OPPh2}(Cl)2]·CHCl3 [22], [Pt{η2Ph2P(OCH(Ph)CH2O}PPh2}(Cl)2]·CHCl3 [22], [Pt{η2-Ph2P (C6H10O2)PPh2}(Cl)2]·CH2Cl2 [23], [Pt{η2-(η2C5H10O2)P{OCH(COOMe)CH(COOMe)O}P(η2-C5H10O2)}(Cl)2] [24], and [Pt{η2-(η2-C17H16NO2)P{OCH(Ph)CH(Ph)O}P(η2-C17H16NO2)](Cl)2]·4CHCl3 (at 150 K) [25]. Structure of [Pt{η2-(η2-C5H10O2)P{OCH (COOMe)CH(COOMe)O}P(η2-C5H10O2)}(Cl)2] [24] is shown in Figure 2 as an example. Each homobidentate-P,P′ donor ligand creates seven-membered metallocyclic rings of the POC2OP type. The mean Pt–L bond distances are 2.221 Å (L = P) and 2.362 Å (Cl). The cis-L–Pt–L bond angles (mean value) open in the order: 87.2° (Cl-Pt-P) < 88.2° (Cl–Pt–Cl) < 97.4° (P-Pt-P). The mean value of the trans-Cl-Pt-P bond angle is 174.3°.

Figure 2 Structure of [Pt{η2-(η2-C5H10O2)P{OCH(COOMe)CH(COOMe)O}P(η2-C5H10O2)}(Cl)2] [24].
Figure 2

Structure of [Pt{η2-(η2-C5H10O2)P{OCH(COOMe)CH(COOMe)O}P(η2-C5H10O2)}(Cl)2] [24].

2.3 Pt(η2-PNC2NP)Cl2 type

There are five examples of this type, which crystallized in two crystal systems: orthorhombic (one example) and monoclinic (four examples). Such complexes are [Pt{η2Ph2P(2,2′-bipyrrolidine)PPh2}(Cl)2] [26], [Pt{η2-Ph2P{N(CH2Ph)CH2CH2(PhCH2)N}PPh2}(Cl)2] [27], [Pt{η2-Pri 2P{N(CH2Ph)CH2CH2N(CH2Ph)}PPri 2](Cl)2] (at 123 K) [28], [Pt{η2-(η2C4H10N2)P{N(Me)(CH2CH2)N(Me)}P(η2-C4H10N2)}(Cl)2] [29], and [Pt{η2-Et2NP(η2-(N2C9H9O)2PNEt2}(Cl)2]·2CHCl3 (at 173 K) [30]. Structure of [Pt{η2-Pri 2P{N(CH2Ph)CH2CH2N(CH2Ph)}PPri 2](Cl2)] [28] is shown in Figure 3 as an example. Each organodiphosphine ligand creates PNC2NP metallocycles with a mean bite angle value of 96.5°. The mean values of the remaining L–Pt–L bond angles are 87.3° (Cl–Pt–Cl), 86.9° and 172.8° (Cl-Pt-P). The mean values of Pt–L bond distance are 2.235 Å (L = P) and 2.360 Å (Cl).

Figure 3 Structure of [Pt{η2-Pri 2P{N(CH2Ph) CH2CH2N(CH2Ph)}PPri 2}(Cl)2] [28].
Figure 3

Structure of [Pt{η2-Pri 2P{N(CH2Ph) CH2CH2N(CH2Ph)}PPri 2}(Cl)2] [28].

2.4 Pt(η2-PSC2SP)Cl2 type

Triclinic [Pt{η2-Ph2P{SC(COOMe)C(COOMe)S}PPh2}(Cl)2]·0.5CH2Cl2 (Figure 4) [31] is the only example of such type. The value of the PSC2SP bite angle is 96.4°. The value of Cl–Pt–Cl bond angle is 87.7° and the mean values of cis- and trans-Cl-Pt-P bond angles are 87.7 and 172.5°, respectively.

Figure 4 Structure of [Pt{η2-Ph2P{SC(COOMe)C(COOMe)S}PPh2}(Cl)2] [31].
Figure 4

Structure of [Pt{η2-Ph2P{SC(COOMe)C(COOMe)S}PPh2}(Cl)2] [31].

2.5 Pt(η2-PNC2OP)Cl2 type

There are five examples of a such type. The orthorhombic [Pt{η2-Ph2P(NC5H9O)PPh2}(Cl)2] exists in two isomeric forms [32,33], monoclinic [Pt{η2-Ph2P(NC5H9O)Pcy2}(Cl)2] (contains two independent molecules) [34], triclinic [Pt{η2-Ph2P{N(Me)CH2CH2O}PPh2}(Cl)2] (at 193 K) [35], and orthorhombic [Pt{η2-(η2-C12H18O2)P(NC5H9O)P(η2-C12H18O2)}(Cl)2]·CH2Cl2 [36].

The structure of [Pt{η2-Ph2P{N(Me)CH2CH2O}PPh2}(Cl)2] [35] is shown in Figure 5 as an example. Each organodisphosphine ligand creates a seven-membered metallocyclic ring (PNC2OP). The values of P-Pt-P bite angles in two isomers are 95.1° [32] and 95.3° [33]. The mean Pt–L bond distances are 2.234 Å (L = P) and 2.354 Å (Cl) in Bandini et al. [32] and 2.236 Å (L = P) and 2.343 Å (Cl) in Naili et al. [33]. Two crystallographically independent molecules within the same crystal in Naili et al. [34] differ from each other in the L–Pt–L bond angles with the values (molecule 1 vs molecule 2): 99.3° (P-Pt-P), 88.0° (Cl–Pt–Cl), 86.5° (Cl-Pt-P) vs 98.9°, 87.8 and 86.7°. The mean Pt–L bond distances (molecule 1 vs molecule 2) are 2.224 Å (L = P) and 2.358 Å (Cl) vs 2.224 and 2.354 Å. The isomers as well as the independent molecules are examples of distortion isomers [6].

Figure 5 Structure of [Pt{η2-Ph2P{N(Me)CH2CH2O}PPh2}(Cl)2] [35].
Figure 5

Structure of [Pt{η2-Ph2P{N(Me)CH2CH2O}PPh2}(Cl)2] [35].

The comprehensive mean values of cis-L–Pt–L bond angles in Bandini et al., Naili et al., and Balakrishna and Mc Donald [32,33,34,35,36] open in the sequence: 87.3° (Cl-Pt-P) < 88.2° (Cl–Pt–Cl) < 97.2° (P-Pt-P). The mean value of trans-Cl-Pt-P bond angles is 174.5°. The total mean values of Pt–L bond distances are 2.227 Å (L = P) and 2.352 Å (Cl).

3 Pt{η2-P(X) n P}Cl2 (n = 5, 6, 7, 8) derivatives

There are over thirty examples of monomeric Pt(ii) complexes in which chelating organodiphosphines create: eight-, nine-, ten-, and eleven-membered metallocyclic rings.

3.1 cis-Pt{η2-P(X)5P}Cl2 type

There are thirteen complexes in which organodiphosphine ligands create eight-membered metallocyclic rings and a pair of chlorides complete a square-planar environment about each Pt(ii) atom with various degrees of distortion. These complexes crystallize in three crystal systems: triclinic (two examples), monoclinic (five examples), and orthorhombic (six examples). In five complexes, namely: [Pt{η2-Ph2P(CH2)5PPh2}(Cl)2] [37], [Pt{η2Ph2P(C13H8O)PPh2}(Cl)2]·2CH2Cl2 (at 100 K) [38], [Pt{η2-Pri 2P(C20H12)PPri 2}(Cl)2]·2CHCl3 (at 173 K) [39], [Pt{η2-Ph2P(C20H12)PPh2}(Cl)2] (at 150 K) [40], and [Pt{η2Ph2P(C12H10)PPh2}(Cl)2]CH2Cl2 [41], the respective chelating organodiphosphine ligands create eight-membered metallocyclic rings (PC5P) with the mean value of P-Pt-P bite angles of 102.2°.

In another five complexes, [Pt{η2-Ph2P(C16H12O)PPh2}(Cl)2]·3.25CH2Cl2 [42], [Pt{η2-Ph2P(C14H12OSi)PPh2}(Cl)2]MeCN (at 150 K) [43], [Pt{η2-(η2-C20H12O2)P(C15H12O)P(η2-C20H12O2)}(Cl)2]MeCN·CH2Cl2 (at 150 K) [44], [Pt{η2-(η2-C22H28O3)P(C15H12O)P(η2-C22H28O3)}(Cl)2] (at 150 K) [45], and [Pt{η2-(η2-C16H12)P(C15H12)P(η2-C16H12)}(Cl)2]CH2Cl2 (at 150 K) [46], the chelating organodiphosphine ligands form eight-membered metallocyclic rings (PC2OC2P) with the mean value of the P-Pt-P bite angles of 100.9°. The structure of [Pt{η2-Ph2P(C14H12OSi)PPh2}(Cl)2] [43] is shown in Figure 6 as an example.

Figure 6 Structure of [Pt{η2-Ph2P(C14H12OSi)PPh2}(Cl)2] [43].
Figure 6

Structure of [Pt{η2-Ph2P(C14H12OSi)PPh2}(Cl)2] [43].

In [Pt{η2-Pri 2P(OC6H10O)PPri 2}(Cl)2] (at 150 K) [47], the chelating P,P-donor ligand creates an eight-membered metallocyclic ring (POC3OP) with the value of P-Pt-P bite angle of 100.2°. In [Pt{η2-Ph2P(CH2)2N(Ph)(CH2)2PPh2}(Cl)2]CH2Cl2 (at 170 K) [48], the chelating P,P-donor ligand creates eight-membered metallocyclic ring (PC2NC2P) with the value of P-Pt-P bite angle of 101.0°. In [Pt{η2-Pri 2P{N(H)N(Me)P(S)(Ph)N(Me)N(H)}PPri 2}(Cl)2] [49], the chelating P,P-donor ligand creates PN2PN2P ring (100.6°).

In these complexes the total mean values of cis-L–Pt–L bond angles open in the sequence: 85.7° (Cl-Pt-P) < 86.4° (Cl–Pt–Cl) < 101.3° (P-Pt-P), and the mean value of trans-Cl-Pt-P bond angles is 172.5°. The total mean value of Pt–L bond distances is 2.248 Å (range 2.235 – 2.262 Å) (L = P) and 2.354 Å (range 2.342 – 2.362 Å) (L = Cl).

3.2 cis-Pt{η2-P(X)6P}Cl2 type

There are nine examples in which chelating organodiphosphine ligands create nine-membered metallocyclic rings. These complexes crystallize in two crystal systems: triclinic (four examples) and monoclinic (five examples). Based on the respective metallocyclic rings these complexes can be divided into the two sub-groups. In the following four complexes, [Pt{η2bnbp}(Cl)2] [50], [Pt{η2-Ph2P(C18H12)PPh2}(Cl)2] [51], [Pt{η2-Pri 2P(C18H24)PPri 2}(Cl)2]·C6H6 (at 120 K) [52] (Figure 7), and [Pt{η2-(η2-C8H12)P(C14H16)P(η2-C8H12)}(Cl)2] [53], the chelating orgnodiphosphine ligands create nine-membered metallocyclic rings (PC6P) with the mean value of P-Pt-P bite angles of 95.0°.

Figure 7 Structure of [Pt{η2-Pri 2P(C18H24)PPri 2}(Cl)2] [52].
Figure 7

Structure of [Pt{η2-Pri 2P(C18H24)PPri 2}(Cl)2] [52].

In the remaining five complexes, [Pt{η2-Ph2P(OC7H10O)PPh2}(Cl)2]·2CH2Cl2 (at 115 K) [54], [Pt{η2-Pri 2P(OC12H8O)PPri 2}(Cl)2] (at 123 K) [55], [Pt{η2-Ph2P(OC12H8O)PPh2}(Cl)2]CH2Cl2 (at 173 K) [55], [Pt{η2-(η2-C10H16O3)P(OC8H8O)P(η2-C10H16O3)}(Cl)2]·CH2Cl2 (at 100 K) [56], and [Pt{η2-(C9H11O)2P(OC20H12O)P(OC9H11)2}(Cl)2]·0.35CH2Cl2.2.3MeCN (at 125 K) [57], each chelating organodiphosphine ligand creates nine-membered metallocyclic ring (POC4OP) with mean value of P-Pt-P bite angles of 95.4°. In this series of complexes, the cis-L–Pt-P bond angles (mean values) open in the sequence: 86.7° (Cl–Pt–Cl) < 89.0° (Cl-Pt-P) < 95.3° (P-Pt-P). The mean value of trans-Cl-Pt-P bond angles is 173.5°. The total mean values of Pt–L bond distances are 2.205 (range 2.185 – 2.220 Å) (L = P) and 2.335 (range 2.323–2.355 Å (L = Cl).

3.3 cis- and trans-Pt{η2-P(X)7P}Cl2 type

In two monoclinic cis-complexes, [Pt{η2-Ph2P{OC10H6(CH2)C10H6O}PPh2}(Cl)2] CH2Cl2.H2O [58] and [Pt{η2-Ph2P{OC6H4(CH)2C6H4O}PPh2(Cl)2]·CH2Cl2 (at 103 K) [59], the chelating organodiphosphine ligands create ten-membered metallocyclic rings of the composition (POC5OP) with the mean values of P-Pt-P bite angles of 95.5° and Cl–Pt–Cl of 89.1°. The mean Pt-P and Pt-Cl bond distances are 2.231 and 2.356 Å, respectively.

A similar ring (POC5OP) was found in monoclinic cis- and triclinic trans-[Pt{η2Pri 2P{OC12H8(CH2)O}PPri 2}(Cl)2]·2CHCl3 (at 173 K) [60]. In the cis-isomer, the values of P-Pt-P and Cl–Pt–Cl bond angles are 95.9 and 85.6°, respectively. The mean values of Pt–L bond distances are 2.247 Å (L = P) and 2.358 Å (L = Cl), respectively. The trans-isomer (Figure 8) contains two crystallographically independent molecules. In trans-isomer, the values of trans-P-Pt-P and trans-Cl–Pt–Cl bond angles (molecule 1 vs molecule 2) are 171.5 and 178.4° vs 170.3 and 177.8°. The mean values of Pt–L bond distances are 2.309 Å (L = P) and 2.307 Å (L = Cl) in molecule 1 and in molecule 2 the values are 2.314 and 2.306 Å, respectively. The Pt-Cl bond distance in the cis-isomer of 2.358 Å is longer than that in the trans-isomer (2.307 Å) as a reason for the higher trans-influence of P over Cl. The sum of all four (Pt-P(x2) + Pt-Cl(x2)) bond distances growing in the order: 9.121 Å (cis-isomer) < 9.232 (trans-molecule 1) < 9.240 Å (trans-molecule 2). This indicates that in the given order the covalent bond is somewhat weak (Pt–L).

Figure 8 Structure of trans-[Pt{η2-Pri 2 P{OC12H8(CH2)O}PPri 2}(Cl)2] [60].
Figure 8

Structure of trans-[Pt{η2-Pri 2 P{OC12H8(CH2)O}PPri 2}(Cl)2] [60].

In orthorhombic cis-[Pt{η2-Ph2P(C23H26O2)PPh2}(Cl)2] [61], the chelating ligand creates ten-membered metallocyclic ring (PC2OCOC2P) with the value of PPt-P bite angle of 96°. In monoclinic cis-[Pt{η2-Ph2P(C6H8O3)PPh2}(Cl)2] [62] the organodiphosphine ligand forms (POC2OC2OP) ring with the value of P-Pt-P bond angle of 96.2°. In triclinic cis-[Pt{η2-Ph2P(C7H6OC7H6)PPh2}(Cl)2]·CH2Cl2 (at 100 K) [63], the organodiphosphine ligand creates a ten-membered metallocyclic ring (PC3OC3P) with P-Pt-P bite angle of 96.5°.

In this series of cis-complexes the cis-L–Pt–L bond angles (mean values) open in the sequence: 87.4° (Cl–Pt–Cl) < 88.5° (Cl-Pt-P) < 95.7° (P-Pt-P). The mean values of Pt–L bond distances are 2.239 (range 2.29 – 2.253) Å (L = P) and 2.354 (range 2.229 – 2.253) Å (L = Cl).

3.4 cis- and trans-Pt{η2-P(X)8P)Cl2 type

In two monoclinic cis-complexes, [Pt{η2-Ph2P(C20H16O2)PPh2}(Cl)2]CDCl3 (at 100 K) [51] and [Pt{η2-Ph2P(C16H14)PPh2}(Cl)2] (at 150 K) (Figure 9) [64], organodiphosphine ligands create eleven-membered metallocyclic rings (PC8P) with the mean P-Pt-P bite angles of 97.0°. In another monoclinic cis-[Pt{η2Ph2P(NC12H8N)PPh2}(Cl)2] (at 125 K) [65], the chelating P,P-donor ligand creates (PNC6NP) metallocyclic ring (97.6°).

Figure 9 Structure of [Pt{η2-Ph2P(C16H14)PPh2}(Cl)2] [64].
Figure 9

Structure of [Pt{η2-Ph2P(C16H14)PPh2}(Cl)2] [64].

Monoclinic [Pt{η2-Pri 2P(OC14H12O)PPri 2}(Cl)2] (at 173 K) [60] exists in two isomeric forms: cis (contains 3CHCl3 solvate) and trans. In both isomers, the chelating ligand creates POC6OP-metallocyclic rings with the values of P-Pt-P bite angles of 96.6° (cis-isomer) and 177.9° (trans-isomer). In cis-isomer, the mean values of Pt-P and Pt-Cl bond distances are 2.237 and 2.376 Å, and Cl–Pt–Cl bond angle is 85.4°. In trans-isomer, the values are 2.323 and 2.305 Å. The value of the trans-Cl–Pt–Cl bond angle is 173.5°.

In this series of cis-complexes, the total mean values of cis-L–Pt–L bond angles are 97.0° (P-Pt-P) and 86.0° (Cl–Pt–Cl). The total mean values of Pt–L bond distances are 2.237 Å (L = P) and 2.370 Å (L = Cl). In trans-derivative, the mean values of trans-L–Pt–L bond angles are 176.2° (P-Pt-P) and 173.2° (Cl–Pt–Cl). The mean values of Pt–L bond distances are 2.320 Å (L = P) and 2.303 Å (L = Cl).

There are 31 examples with cis-configuration and 3 examples with trans-configuration. The total mean values of Pt–L bond distances in the complexes (cis- vs trans-configuration) are 2.232 Å (L = P), 2.353 Å (L = Cl) vs 2.312, and 2.307 Å, respectively.

3.5 Pt{η2-P(X) n P}Cl2 (n = 10, 11, 15, 18) type

Chelating ligand in cis-[Pt{η2-Ph2P(C20H10N2O2)PPh2}Cl2], which exists in monoclinic [66] and orthorhombic [67] classes, forms 13-membered metallocyclic rings of the (PC3NC2NC3P) type with the values of P-Pt-P bite angles of 101.1 and 98.9°, respectively. The sum of the four Pt–L bond distances are 9.14 and 9.31 Å. These values suggest, that the inner coordination sphere about the Pt(ii) atom in the orthorhombic isomer is less crowded than in its monoclinic partner. These isomers are examples of distortion isomerism.

In two monoclinic isomers cis- and trans-[Pt{η2-Ph2P(C8H16O3)PPh2}Cl2] [68] the chelating ligand creates fourteen-membered metallocyclic rings of (PC2OC2OC2OC2P) type, with the values of P-Pt-P bite angles of 98.7 and 173.0°, respectively. The Pt–L bond distances mean values cis- vs trans-isomers are 2.246 Å (L = P) and 2.346 Å (Cl) vs 2.313 Å (P) and 2.297 Å (Cl).

In other isomers, orthorhombic cis- and monoclinic trans-[Pt{η2-Ph2P(C22H25N3)PPh2}Cl2] [69], the chelating ligand creates 18-membered metalocyclic ring of (PC4NC2NC4P) type with the values of P-Pt-P bite angles of 98.3 and 178.3°, respectively. The Pt–L bond distances (mean values) cis- vs trans-isomers are: 2.255 Å (L = P) and 2.345 Å (Cl) vs 2.309 Å (P) and 2.300 Å (Cl).

The total mean values of Pt–L bond distances in cis- vs trans-isomers are 2.250 Å (L = P) and 2.340 Å (Cl) vs 2.311 Å (P) and 2.298 Å (Cl). The Pt-Cl bond distance in cis-complexes is longer (weaker) than in trans-partner, as a reason for the stronger trans-influence of P donor ligand over Cl. The sum of four Pt–L bond distances is 9.192 Å in cis- and 9.218 Å vs trans-partners. The cis-complex is somewhat more crowded than its trans-partners.

Triclinic cis-Pt{η2-Ph2P(C22H28N2O2)PPh2}Cl2 [70] contains two crystallography-independent molecules within the same crystal. The structure of one molecule is shown in Figure 10. The chelating ligand forms a 21-membered metallocycle (POC2NC10NC2OP) with the values of P-Pt-P bite angles of 94.2 and 93.2°, respectively. One will be expecting more open bite angles. The reason can be that the macrocycle is twisted. The independent molecules differ from each other only by small variation of Pt–L bond distances 2.220 Å (L = P), 2.359 Å (Cl) (module 1) vs 2.232 and 2.355 Å (module 2).

Figure 10 Structure of Pt{η2-Ph2P(C22H28N2O2)PPh2}Cl2 [70].
Figure 10

Structure of Pt{η2-Ph2P(C22H28N2O2)PPh2}Cl2 [70].

4 Conclusions

This structural study together with its precursors [3] summarized, analyzed, and classified structural parameters of 200 monomeric Pt(ii) complexes of the general formula Pt{η3-P(X) n P}Cl2 (n = 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 15, 18). Homobidentate organodiphosphine via P,P′ donor atoms with a pair of Cl anions build up a distorted square planar geometry about each Pt(ii) atom. To our knowledge, such a series is unique, not only from several metallocycles but also from the member of atoms involved between P, PL donor atoms. There are 12 membered metallocycles with 33 types. 4 – PCP, PNP, 5 – PC-CP, PC=CP, PNNP, PCOP, 6 – PC3P, PNCNP, PCCOP, PCCNP, PCNCP, PCSCP, PCSiCP; 7 – PC4P, POC2OP, PNC2NP, PSC2SP, PNC2OP; 8 – PC5P, PC2OC2P, PC2NC2P; 9 – PC6P, POC4OP; 10 – POC5OP, PC2OCOC2P, PC3OC3P; 11 – PC8P, PNC6CP, POC6OP; 13 – PC3NC2NC3P; 14 – PC2OC2OC2OC2P; 18 – PC4NC2NC2NC4P; and 21 – POC2NC10NC2OP. The total mean values of selected structural data of cis-Pt{η2-P(X) n P}Cl2 derivates are gathered in Table 1.

Table 1

The total mean values of selected structural parameters of cis-Pt{P(X) n P}Cl2 derivatives

Metallocyclic ring (number of examples) P-Pt-P (°) Cl–Pt–Cl (°) Cl-Pt-P (°) Pt-P (Å) Pt-Cl (Å) ∑Pt–L(x4) (Å)
Four membered (24) 72.4 91.7 97.3 2.214 2.352 9.13
170.4
Five membered (61) 86.4 88.0 92.7 2.216 2.354 9.14
175.7
Six membered (42) 94.0 87.6 89.0 2.222 2.358 9.16
175.6
Seven membered (34) 96.8 87.2 87.7 2.239 2.350 9.17
173.5
Eight membered (12) 101.3 86.4 85.7 2.248 2.354 9.20
172.5
Nine membered (9) 95.0 86.7 89.0 2.205 2.335 9.08
173.5
Ten membered (7) 95.7 87.4 88.5 2.239 2.354 9.18
174.0
Eleven membered (6) 97.3 86.0 88.4 2.237 2.370 9.21
175.0
Thirteen membered (2) 100.0 85.0 87.5 2.259 2.366 9.25
170.0
Fourteen membered (11) 98.8 87.8 87.5 2.246 2.346 9.18
188.9
Eighteen membered (1) 98.6 88.5 86.3 2.255 2.345 9.20
Twenty-one membered (1) 93.7 87.8 89.2 2.229 2.357 9.17

As can be seen, there are cooperative effects between cis-L–Pt–L bond angles, the P-Pt-P bite angles growing with the size of metallocyclic ring from four-to-eight membered and the remaining cis-Cl–Pt–Cl and cis-P-Pt-Cl bond angles closes. The sum of all four (Pt-P(x2) + PtCl (x2)) bond distances smoothly growing with the size of respective metallocycles.

No such trends were found for the complexes with higher-membered metallocyclic rings.

One of the reasons can be a “twist” of the respective metallocycles.

There are at least two contributing factors to the size of the L–Pt–L bond angles, both ligands-based. One is the steric constraints imposed on the ligand and the other is the need to accommodate appropriate bidenticity.

The orthorhombic [Pt{η2-Ph2P(NC5H9O)PPh2}(Cl)2] which exists in two isomeric forms [32,33] and monoclinic [Pt{η2-Ph2P(NC5H9O)Pcy2}(Cl)2] which contains two crystallographically independent molecules within the same crystal [34] are classical examples of distortion isomers [6].

The [Pt{η2-Pri 2P{OC12H8(CH2)O}PPri 2}(Cl)2] [60] exists in two isomeric forms: monoclinic cis and triclinic trans. The trans-isomer contains two crystallographically independent molecules that differ mostly by degree of distortion. These complexes belong to the unusual combination of isomerism, cis, trans, and distortion [66]. Monoclinic [Pt{η2-Pri 2P{OC14H12)PPri 2}(Cl)2] [60] exists in two isomeric forms cis and trans.

The mean Pt-Cl and Pt-P bob distances at 2.353 and 2.232 Å, respectively, for cis and 2.307 and 2.312 Å, respectively, for trans. The cis-derivatives tend to be more crowded than the trans-derivatives as seen by comparing the sum of the Pt–L bond distances at 9.17 and 9.25 Å, respectively.

During the collection and organization of the data has become evident that some original papers are lacking important information such as atomic coordinates and analysis of intermolecular distances. Given these limitations, we believe that a structural study like this one can continue to serve a useful function by centralizing available material and delineating areas worthy of further investigation.

Acknowledgments

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. and P.M.; data curation, M.M.; writing – review and editing, V.M. and P.M.; 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: Authors state no conflict of interest.

  4. Data availability statement: The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

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Received: 2024-04-12
Accepted: 2024-06-01
Published Online: 2024-07-11

© 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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https://doi.org/10.1515/mgmc-2024-0005
Keywords for this article
structure; Pt(η2-P(X) n P)(Cl)2 (n = 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 15, 18); organodiphosphines; isomers
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Articles in the same Issue

  1. Research Articles
  2. Mitigation of arsenic and zinc toxicity in municipal sewage sludge through co-pyrolysis with zero-valent iron: A promising approach for toxicity reduction of sewage sludge
  3. Magnetite nanoparticles (Fe3O4 NPs) performed by the co-precipitation and green synthesis processes
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