Band 44, Heft 1

N.N'-Diphenylformamidinato gold(I) (1) is obtained from Na(PhNCH NPh) and Aul in liquid ammonia. It can be recrystallized from toluene/n-heptane to form colorless monoclinic crystals, the space group C 2/c, with the lattice constants a = 1781.7(7), b = 1159.0(5), c = 2518.7(8) pm, β = 99.06(3)°. 1 is tetrameric in solution and in the solid state. In the tetrameric complex with the symmetry C 2 the four Au atoms form a planar rhombus with Au -Au distances between 295,7 and 322.7 pm. The amidinato ligands are arranged alternatively above and below the Au 4 -rhombus and function as bridging ligands for neighbouring Au atoms, which thereby reach a linear coordination with distances A u -N between 200.0 and 202.4 pm.

trans-Dichloro(ethanedial-dioximato)(ethanediaI-dioxime)rhodium (III), RhCl 2 (GH)(GH 2 ), has been synthesized and its structure determined by single crystal X-ray diffraction at room temperature. C 4 H 7 Cl 2 N 4 O 4 Rh, M r = 348.94. monoclinic space group P2 1 /ɑ; a = 10.543(3), b = 8.363(2), c = 11.512(3)Å ; β = 92.79(2)°; V = 1024Å 3 ; Z = 4; D c = 2.26 Mg m -3 . Final R w = 0.075 for 2035 reflections and 139 parameters. The coordination geometry around Rh is a dis­torted (4+2) octahedron, with four chelating N atoms lying in the equatorial plane and the two Cl atoms in the apical positions. The H atoms of the oxime groups are involved in relatively weak intramolecular O-H-O bridgings, as well as in very strong intermolecular bridgings which extend throughout the crystal structure and propagate nearly parallel to the [101] crystallographic direction.

(2) The structure of [t-Bu 3 PI][W(CO) 4 I 3 ] has been determined by X-ray diffraction. The anion of 2 consists of a CO-capped distorted octahedron. One iodine atom of the anion acts as donor towards the iodophosphonium cation. In 2 the I···I interaction is weaker and the P-I bond is stronger than in t-Bu 3 PI 2 . Structural features of t-Bu 3 PI ⊕ cations are compared with those of the isoelectronic molecule t-Bu 3 P = Te.

The ionization potentials of sulfurtetrafluoride have been measured using threshold photoelectron spectroscopy and com pared with theoretical calculations. The decay of SF 4 + has been studied by photoionization mass spectrometry and photoion-photoelectron coincidence. The break-down graphs reveal competing decay processes. Bond dissociation energies in SF 4 + have been calculated.

The ionization potential of CH 3 SCF 3 and the appearance potentials of fragment ions have been measured in the photon energy range 9 -19 eV using synchrotron, radiation. From these results thermochemical data of CH 3 SCF 3 , CH 3 SCF 3 + and fragment ions have been evaluated.

The appearance potentials of fragment ions from SF 5 Cl have been measured in the energy range 12 - 20 eV by means of photoionization mass spectrometry. From these data, the ionization potential of SF 5 comes to 9.65 eV.

Dithiocarbimates. Sulfonamides, X-Ray. Sulfones By reaction of the sulfonamides C 6 H 5 -SO 2 -NH 2 and p-Cl-C 6 H 4 -SO 2 -NH 2 with CS 2 in the presence of bases the corresponding dithiocarbimates have been obtained in form of their potassium salts and characterized by means of X-ray structural analysis. Both compounds crystallize in the space group P2 1 /a with a = 29.778(3), b - 6.202(1). c = 7.169(1) Å and β = 90.33(2)° for K 2 [S 2 C = N-SO 2 -C 6 H 5 ] · 2H 2 O and a = 31.517(3). b = 7.189(1), c -6.196(1) Å and β = 90.10(1)° for the Cl-substituted species, respectively. A relation between both crystal structures becomes obvious when for K 2 [S 2 C = N-SO 2 -C 6 H 4 -Cl] · 2H 2 O the first space group setting is choosen; i.e. P 1 1 2 1 /a. The dithiocarbimates are built up of two planar moieties. One plane contains the S 2 C = N-SO framework of each anion while a second plane consists of the S-C 6 H 5 group and the S-C 6 H 4 -Cl group, respectively. The two planes are oriented nearly perpendicular to each other and give rise to conjugation involving the SO 2 groups in the different systems.

By reaction of K 2 [S 2 CNSO 2 C 6 H 5 ] · 2H 2 O and K 2 [S 2 CNSO 2 C 6 H 4 Cl] · 2H 2 O, respectively, with Ni(CH 3 COO) 2 · 4H 2 O the complex anions [Ni(S 2 C = N-(SO 2 -C 6 H 5 ) 2 ] 2- and [Ni(S 2 C = N-SO 2 -C 6 H 4 -Cl) 2 ] 2- are formed and have been isolated in form of their (PPh 4 ) salts. (PPh 4 ) 2 [Ni(S 2 C = N-SO 2 -Ph) 2 ] crystallizes monoclinicly. space group P2 1 /a with a = 19.081(4), b = 9.106(1), c = 17.630(4) Å and β = 113.42(6)° with Z = 2. (PPh 4 ) 2 [Ni(S 2 C = N-SO 2 -C 6 H 4 -Cl) 2 ] · 2H 2 O crystallizes triclinicly, and the non-standard setting Cl has been choosen with a = 15.732(3), b = 22.509(4), c = 9.521(1) Å , ɑ = 96.30(6), β = 117.57(9), γ = 88.93(5)° and Z = 2. Within the complex anions nickel has the site-symmetry 1 and is coordinated by four sulfur atoms with Ni-S mean = 2.198 Å. The Ni(S 2 C = N-SO) 2 units are essentially planar in both systems. This planarity gives rise to conjugation effects involving the SO 2 group and the π-system of S 2 C = N - as well as the lone pair on N.

S,S-Dimethylsulfoximinato-diphenyl-N-trimethylsilylphosphoranylidenamin (1) reacts in a molar ratio of 1:1 with TiCl 4 , CpTiCl 3 , (Cp = C 5 H 5 ), VOCl 3 , and Cp*TaCl 4 (Cp* = C 5 Me 5 ) to yield the 1:1 adduct 1 · TiCl 4 (2) and the substituted products Me 2 S(O) = NPPh 2 = N-TiCpCl2 (3), Me 2 S(O) = NPPh 2 =N-VOCl 2 (4) and Me 2 S(O) = NPPh 2 = N-TaCp*Cl 3 (5). The structures of 3, 4 and 5 show short metal-nitrogen bond lengths.

Dichlorophenylphosphine reacts with two equivalents of dibenzoylmethane at -30 °C in the presence of triethylamine to give a tricyclic phosphorane intermediate 4 which isomerizes to the more stable phosphinic acid ester 5 above 30 °C. The structures of 4 and 5 were determined by 13 C, 1 H shift correlated 2D NMR spectroscopy using long range couplings.

The diborylated sulfamide 6a can be obtained from 2-chloro-1,3-dimethyl-1,3,2-diazaborolidine and the silylated sulfamide la , whereas (Me 2 N) 2 BCl and 1a yield the dithia-tetrazadiborocine 7b. Similarly, (Me 2 N) 2 BCl reacts with a) the sulfonimine 2a, b) the sulfonediimine 3a to give a) B(NMe 2 ) 3 , and the bis-and tris(sulfonimino)boranes 10b and 11, b) B(NMe 2 ) 3 and the dithiatetrazadiborocine 15b. The diborylated sulfamide 6c (R 2 B = Ph 2 B) cannot be isolated. The synthesis of the monoborylated sulfonimines 9c, 9e and sulfonediimines 13, 14 is described.

13 C and 15 N NMR data are reported for the free aminophosphanes ʹBu 3-n P(NH 2 ) n (n = 1 (1), 2 (2)), for the corresponding pentacarbonylchromium complexes (OC) 5 Cr-P(ʹBu) 3-n (NH 2 ) n (n = 1 (3), n = 2 (4), n = 3 (5)), and for other (OC) 5 Cr-aminophosphane complexes such as (OC) 5 Cr-P(NMe 2 ) 3 , (6 ) and a binuclear complex (7) in which the sulfurdiimide derivative ʹBu(NH 2 )P-NSN-P(NH 2 )ʹBu serves as the phosphane ligand. Various techniques (e.g. INEPT and reverse two-dimensional (2D) 1 H { 15 N}-experiments) have been used for recarding the 15 N NMR spectra at natural abundance. In contrast to suggestions in the literature, the relationship between the 13 C NMR parameters for the axial and equatorial CO groups and the σ-donor/π-acceptor properties of the phosphane ligand is not straightforward. The 15 N resonances of the (OC) 5 Cr complexes 3, 4, 6 are shifted to higher frequencies with respect to those of the free ligands, and there is a regular decrease in 15 N nuclear shielding in the series of 3, 4, 5. The | 1 J( 31 P 15 N)| values vary between 17 and 65 Hz, the smaller values being observed for the (OC) 5 Cr complexes. The lack of a regular change in the magnitude of 1 J( 31 P 15 N) in the series 3, 4, 5 indicates that this parameter is influenced by the nature of both the Cr-P and the P-N bonds as a function of the number of amino groups.

By analyzing the phase diagrams of some trimethylhalogenosilane/pyridine- and methyl-trichlorosilane/lutidine-systems the existence of the incongruently melting addition compounds Me 3 SiF · (Pyridine) 2 , Me 3 SiCl · (Pyridine) 2 , MeSiCl 3 , · (2.5-Lutidine) 2 , MeSiCl 3 , · (2.6-Lutidine) 2 , (MeSiCl 3 ) 2 · 3.5-Lutidine, and the congruently melting compounds MeSiCl 3 · 2.4-Lutidine, MeSiCl 3 · (3.5-Lutidine) 2 was proven.

The reaction of anisole with Na/K-alloy and subsequent reaction with dichloro(diisopropyl-amino)borane yields diisopropylamino(diphenoxy)borane (1). In reacting the sodium complex of 1-or 2-m ethoxynaphthalene, respectively, with dichloro(diorganylamino)boranes the ether bond is cleaved. One obtains the methoxy-2-naphthoxy-diorganylam inoboranes (2a -d) besides the di-2-naphthoxy-diorganylam inoboranes (3a-e), the 2-naphthoxy-bis(diorganylamino)boranes (4a-b) and the solvated sodium-2-naphtholate (6). By-products are 1,2-bis[(diisopropylamino)-1- or 2-naphthoxyboryl]ethyne derivatives 5a and 5b, terized analytically and spectroscopically (MS; NMR: 1 H, 11 B, 13 C).

Infrared and Raman spectra of the metal cluster compound [Nb 6 F 12 ]F 3 (cubic Im3̄m; Z = 2) are reported. The three intense m odes observed in the Raman spectrum at 215. 267, and 337 cm -1 and a weak mode observed in the infrared spectrum at 287 cm -1 are assigned to the T 2g , E g , A 1g , and T 1u vibrational modes of the Nb 6 octahedra. The assignment is supported by normal coordinate analysis and Raman measurements at 47 kbar. The valence force constants are f(Nb-F i ) = 2.04, f(Nb-F a-a ) = 1.30 and f(Nb-Nb) = 0.97 N cm -1 metal-to-metal interaction in the cluster.

The substitution of 4 CO ligands in Ir4(CO) 12 by tris-(2-carbethoxyethyl)phosphine and sub­ sequent reaction with ammonia yielded water soluble Ir clusters which when modified further can be used for heavy atom labelling of proteins.

Aerosils, Onium Groups. Interparticular "cross-linking" Aerosils with covalently linked onium group 2a-f catalyze the exchange of halogene (Finkel-stein-Reaction) and migrate in an electric field depending on the nature of the end groups and the kind of the suspension medium. Electroactive groups covalently linked with aerosil are electroreduced on mercury and lead cathodes. The possibility of an interparticular cross linking is demonstrated.

Treatment of indium trichloride with three equivalents of the cyclopentadienyliron carbonyl anions, [Fe(CO) 2 (η-C 5 H 4 R)] - (R = H, Me) affords the tri-iron indium complexes [In {Fe(CO) 2 (η-C 5 H 4 R)} 3 ] (R = H, Me) as dark red crystalline materials. Both compounds were characterized by spectroscopic and analytical methods. Infrared spectroscopy indicates that both complexes are undissociated in solution in contrast to previously reported analogous molybdenum containing species.

(MeCp) 2 Ti(NCO)(NCNSiMe 3 ) (1), Cp 2 Ti(NCO)(NCNSiMe 3 ) (2) and Cp 2 Ti(NCNSiMe 3 ) 2 (3) are formed by the reaction of (MeCp)Ti(NCO) 2 and Cp 2 Ti(NCO) 2 with LiN(SiMe 3 ) 2 . All three new com pounds are thermally and hydrolytically unstable red solids that were characterized by mass spectrometry. 1 H NMR and elemental analysis.

Dimerization of 1,2-bis(diisopropylamino)-1 ,2-dihydro-1,2-diborete (2) with palladium phthalocyanine quantitatively yields the eight-membered 1,2,5,6-tetrakis(diisopropylamino)-1,2,5,6-tetrahydro- 1,2,5,6-tetraborocine (3), which thermally or photolytically rearranges to give 2,4,6,8-tetrakis- (diisopropylamino)-2,4,6.8-tetrabora-tricyclo- [3,3,0,0 3,7 ]-octane (4). The X-ray structure analysis of the S 4 N 4 -like cage 4 exhibits long C-C-distances (1.67(1) Å ). 4 crystallizes in the space group F2dd with the lattice constants: a = 7.432(2), b = 24.802(6), c = 36.563(9) Å.

The title compound 3 obtained by the Knoevenagel condensation of t-butyl acetoacetate (1) with methylthioethanal (2) in the presence of zinc chloride was found to undergo an easy isomerization on silica gel to its β,γ-isomer which exists as a mixture of the keto (4) and enol (5) forms.

Phase equilibrium studies of the Lewis acid-base systems AlCl 3 /PyHBr and AlBr 3 /PyHI indicate the existence of congruently melting compounds of the molar ratios 1:1 and 2:3. These results are quite different from those of our studies of the AlCl 3 /PyHCl and the AlBr 3 /PyHBr systems, in which four compounds in the molar ratios 1:1, 1:2, 1:3, and 2:3 could be detected. The melting point of pyridinium iodide observed at 284,8 °C (decomp.) differs from the previously reported one.