Die Kristallstruktur von p-Tolylbis(diethyldithiocarbamato)-thallium(III) und Phenylbis(methylxanthogenato)bismut(III)

Crystal Structure of p-Tolylbis (diethyldithiocarbamato)thallium(III) and Phenylbis-(methylxanthogenato)bismut(III) The crystal structure of 4-CH₃(C₆H₄)? Tl(S₂CN(C₂H₅)₂)₂ (P2₁/c, a = 11.973(3), b = 10.692(3), c = 19.232(4) Å, β = 114.02(2)°, Z = 4) and C₆H₅-Bi(S₂COCH₃)₂ (P2₁/c, a = 6.395(2), b = 24.684(8), c = 9.732(3) Å, β = 101.38(3)°, Z = 4) was solved from X-ray diffraction data of single crystals. From the interatomic distances follows that the dithiocarbamate and xanthogenate ligands coordinate asymmetrically bidentate to the metal as presumed and exclusively through the sulfur atoms. Differences in the coordination sphere of bismut and thallium give evidence for a “stereochemically active lone pair” on the bismut atom.     

Neue Phosphor-verbrückte Übergangsmetallcarbonyl-Komplexe Die Kristallstrukturen von [Re2(CO)7(PtBu)3], [Co4(CO)10(PtBu)2], [Ir4(CO)6(PtBu)6] und [Ni4(CO)10(PiPr)6]

New Phosphorus-bridged Transition Metal Carbonyl Complexes. The Crystal Structures of [Re₂(CO)₇(P^tBu)₃], [Co₄(CO)₁₀(P^tBu)₂], [Ir₄(CO)₆(P^tBu)₆], and [Ni₄(CO)₁₀(PⁱPr)₆], (P^tBu)₃ reacts with [Mn₂(CO)₁₀], [Re₂(CO)₁₀], [Co₂(CO)₈] and [Ir₄(CO)₁₂] to form the multinuclear complexes [M₂(CO)₇(P^tBu)₃] (M = Re ( 1 ), Mn ( 5 )), [Co₄(CO)₁₀(P^tBu)₂] ( 2 ) and [Ir₄(CO)₆(P^tBu)₆] ( 3 ). The reaction of (PⁱPr)₃ with [Ni(CO)₄] leads to the tetranuclear cluster [Ni₄(CO)₁₀(PⁱPr)₆] ( 4 ). The complex structures were obtained by X-ray single crystal structure analysis: ( 1 : space group P1 (Nr. 2), Z = 2, a = 917.8(3) pm, b = 926.4(3) pm, c = 1 705.6(7) pm, α = 79.75(3)°, β = 85.21(3)°, γ = 66.33(2)°; 2 : space group C2/c (Nr. 15), Z = 4, a = 1 347.7(6) pm, b = 1 032.0(3) pm, c = 1 935.6(8) pm, β = 105.67(2)°; 3 : space group P1 (Nr. 2), Z = 4, a = 1 096.7(4)pm, b = 1 889.8(10)pm, c = 2 485.1(12) pm, α = 75.79(3)°, β = 84.29(3)°, γ = 74.96(3)°; 4 : space group P2₁/c (Nr. 14), Z = 4, a = 2 002.8(5) pm, b = 1 137.2(8) pm, c = 1 872.5(5) pm, β = 95.52(2)°).     

(Phosphine)gold(I) Complexes of Benzenedithioles. Crystal structures of 1,2-benzenedithiolato-bis[triphenyl-phosphinegold(I)] and bis(triethylphosphine)gold(I) bis(1,2-benzenedithiolato)gold(III)

The reaction of 1,2- and 1,3-benzenedithiol C₆H₄(SH)₂ with chloro(phosphine)gold(I) complexes R₃PAuCl (R = Et, Ph) in the presence of triethylamine in tetrahydrofuran gives stable gold(I) complexes 1,2-C₆H₄(SAuPR₃)₂ [R = Et ( 1 ) and Ph ( 2 )] or 1,3-C₆H₄(SAuPPh₃)₂ ( 3 ), respectively, in high yield. The compounds have been characterized by analytical and NMR spectroscopic data. From the reaction of 1,2-C₆H(SH)₂ with Et₃P? AuCl a by-product [(Et₃P)₂Au]⁺ [Au(1,2? C₆H₄S₂)₂]^? ( 4 ) has also been isolated in low yield. The crystal structures of compounds 2 and 4 have been determined by single crystal X-ray diffraction. The gold(I) atoms in complex 2 are two-coordinate with bond angles S? Au? P of 175.2(1) and 159.5(1)°, Au? S bond distances of 2.304(1) and 2.321(1) å, and a short Au…?Au contact of 3.145(1) Å. The gold(I) atom in the cation of complex 4 is also linearly two-coordinate with a P? Au? P angle of 170.1(1) Å and Au? P distances of 2.296(3) and 2.298(3) Å. The geometry of the anion in 4 shows a square-planar coordination of gold(III) by two chelating 1,2-benzenedithiolate ligands with Au? S distances between 2.299(3) and 2.312(3) Å (for two crystallographically independent, centrosymmetrical anions in the unit cell).     

Darstellung,Strukturen und EPR-Spektren der Rhenium(II)-Nitrosylkomplexe [Re(NO)Cl2(PPh3)(OPPh3)(OReO3)], [Re(NO)Cl2(OPPh3)2(OReO3)] und [Re(NO)Cl2(OPPh3)3](ReO4)

Synthesis, Structures, and EPR-Spectra of the Rhenium(II) Nitrosyl Complexes [Re(NO)Cl₂(PPh₃)(OPPh₃)(OReO₃)], [Re(NO)Cl₂(OPPh₃)₂(OReO₃)], and [Re(NO)Cl₂(OPPh₃)₃](ReO₄) The paramagnetic rhenium(II) nitrosyl complexes [Re(NO)Cl₂(PPh₃)(OPPh₃)(OReO₃)], [Re(NO)Cl₂(OPPh₃)₂ · (OReO₃)], and [Re(NO)Cl₂(OPPh₃)₃](ReO₄) are formed during the reaction of [ReOCl₃(PPh₃)₂] with NO gas in CH₂Cl₂/EtOH. These and two other Re^II complexes with 5 d⁵ ”︁low-spin”︁”︁-configuration can be observed during the reaction EPR spectroscopically. Crystal structure analysis shows linear coordinated NO ligands (Re–N–O-angles between 171.9 and 177.3°). Three OPPh₃ ligands are meridionally coordinated in the final product of the reaction, [Re(NO)Cl₂(OPPh₃)₃][ReO₄] (monoclinic, P2₁/c, a = 13.47(1), b = 17.56(1), c = 24.69(2) Å, β = 95.12(4)°, Z = 4). [Re(NO)Cl₂(PPh₃)(OPPh₃)(OReO₃)] (triclinic P 1, a = 10.561(6), b = 11.770(4), c = 18.483(8) Å, α = 77.29(3), β = 73.53(3), γ = 64.70(4)°, Z = 2) and [Re(NO)Cl₂ (OPPh₃)₂(OReO₃)] (monoclinic P2₁/c, a = 10.652(1), b = 31.638(4), c = 11.886(1) Å, β = 115.59(1)°), Z = 4) can be isolated at shorter reaction times besides the complexes [Re(NO)Cl₃(Ph₃P)₂], [Re(NO)Cl₃(Ph₃P) · (Ph₃PO)], and [ReCl₄(Ph₃P)₂].     

Polysulfonylamine. XL Darstellung von Silber(I)-disulfonylamid-Acetonitril-Komplexen. Röntgenstrukturanalytische und thermochemische Charakterisierung von Tetraacetonitrilsilber(I)-bis(dimesylamido)argentat(I) und von (1,1,3,3-Tetraoxo-1,3,2-benzodithiazolido)acetonitrilsilber(I)

Polysulfonyl Amines. XL. Preparation of Silver(I) Disulfonylamide Acetonitrile Complexes. Characterization of Tetraacetonitrilesilver(I) bis(dimesylamido)argentate(I) and (1,1,3,3-Tetraoxo-1,3,2-benzodithiazolido)acetonitrilesilver(I) by X-Ray Diffractometry and Thermal Analysis The following silver(I) disulfonylamides were prepared for the first time or by improved procedures: AgN(SO₂CH₃)₂ ( 2a ); AgN(SO₂C₆H₄-4-X)₂ with X = F ( 2b ), Cl ( 2c ), Br ( 2d ), CH₃ ( 2e ); silver(I) 1,2-benzenedisulfonimide AgN(SO₂)₂C₆H₄ ( 2f ). With acetonitrile, the salts 2a to 2e form (1/2) complexes AgN(SO₂R)· 2 CH₃CN ( 4a to 4e ), whereas 2f gives the (1/1) complex AgN(SO₂)₂C₆H · CH₃CN ( 4f ). The crystallographic data (at - 95°C) for the title compounds 4a and 4f are: 4a , space group C2/c, a = 1 967.6(4), b = 562.2(1), c = 2 353.0(5) pm, β = 102.21(2)°, V = 2.5440 nm³, Z = 4, D_x = 1.891 Mg m^?3; 4f , space group P2₁/m, a = 741.5(3), b = 980.4(4), c = 756.6(3) pm, β = 99.28(2)°, V = 0.5428 nm³, Z = 2, D_x = 2.246 Mg m^?3. 4a forms an ionic crystal [Ag(NCCH₃)₄]^⊕[Ag{N(SO₂CH₃)₂}₂]^? with a tetrahedrally coordinated silver atom (lying on a twofold axis) in the cation (225.3/225.7 pm for the two independent Ag? N distances, N? Ag? N 106.2—114.5°) and a linear-dicoordinated silver atom in the centrosymmetric anion (Ag? N 213.9 pm, two intraionic secondary Ag…O contacts 303.4 pm). 4f consists of uncharged molecules [C₆H₄(SO₂)₂N¹AgN²CCH₃] with crystallographic mirror symmetry (Ag? N¹ 218.8, Ag? N² 216.1 pm, N¹? Ag? N² 174.3°), associated into strands by intermolecular secondary silver-oxygen contacts (Ag…O 273.8 pm, O…Ag…O 175.6, N? Ag…O 91.9/88.2°). The thermochemical behaviour of 4f was investigated using thermogravimetry, differential scanning calorimetry (DSC), time- and temperature-resolved X-ray diffractometry (TXRD), and solution calorimetry. The desolvation process occurs in the temperature range from 60 to 200°C and appears to be complex, although no crystalline intermediate could be detected. The desolvation enthalpy at 298 K was found to be + 26.8(4) kJ mol^?1. 4a is desolvated in two steps at - 15 to 60°C and 60 to 95°C (DSC), suggesting the formation of AgN(SO₂CH₃) · CH₃CN as an intermediate.     

Synthese und Strukturen neuer selenido‐ und selenolatoverbrückter Kupfercluster: [Cu38Se13(SePh)12(dppb)6] (1), [Cu(dppp)2][Cu25Se4(SePh)18(dppp)2] (2), [Cu36Se5(SePh)26(dppa)4] (3), [Cu58Se16(SePh)24(dppa)6] (4) und [Cu3(SeMes)3(dppm)] (5)

Syntheses and Crystal Structures of new Selenido‐ and Selenolato‐bridged Copper Clusters: [Cu₃₈Se₁₃(SePh)₁₂(dppb)₆] (1), [Cu(dppp)₂][Cu₂₅Se₄(SePh)₁₈(dppp)₂] (2), [Cu₃₆Se₅(SePh)₂₆(dppa)₄] (3), [Cu₅₈Se₁₆(SePh)₂₄(dppa)₆] (4), and [Cu₃(SeMes)₃(dppm)] (5) The reactions of copper(I) chloride or copper(I) acetate with monodentate phosphine ligands (PR₃; R = organic group) and Se(SiMe₃)₂ have already lead to the formation of CuSe clusters with up to 146 copper and 73 selenium atoms. If the starting materials and the bidentate phosphine ligands (Ph₂P–(CH₂)_n–PPh₂, n = 1: dppm, n = 3: dppp, n = 4: dppb; Ph₂P–C≡C–PPh₂: dppa) and silylated chalcogen derivates are changed (RSeSiMe₃; R = Ph, Mes) a series of new CuSe clusters can be synthesized. From single crystal X‐ray structure analysis one can characterise [Cu₃₈Se₁₃(SePh)₁₂(dppb)₆] ( 1 ), [Cu(dppp)₂] · [Cu₂₅Se₄(SePh)₁₈(dppp)₂] ( 2 ), [Cu₃₆Se₅(SePh)₂₆(dppa)₄] ( 3 ), [Cu₅₈Se₁₆(SePh)₂₄(dppa)₆] ( 4 ) and [Cu₃(SeMes)₃(dppm)] ( 5 ). In this new class of CuSe clusters, compounds 1 and 4 possess a spherical cluster skeleton, wheras 2 and 3 have a layered cluster core.     

Tin(II) aminoalkoxides and heterobimetallic derivatives: the structures of Sn6(O)4(dmae)4, Sn6(O)4(OEt)4 and [Sn(dmae)2Cd(acac)2]2

Tin(II) methoxide reacts with N,N′‐dimethylaminoethanol (dmaeH) to yield Sn(dmae)₂ ( 1 ) along with small amounts of the hydrolysis product Sn₆(O)₄(dmae)₄ ( 2 ). The geometrically more regular iso‐structural cage Sn₆(O)₄(OEt)₄ ( 3 ) was obtained as the only tractable product isolated from reaction of 2 and Sb(OEt)₃, while 1 reacted with CdX₂ (X = acac, I) to afford Sn(dmae)₂Cd(acac)₂ ( 4 ) and Sn(dmae)₂CdI₂ ( 5 ). The X‐ray structures of 2, 3 and 4 are reported. Decomposition of 4 under aerosol‐assisted chemical vapour deposition conditions leads to amorphous tin oxide films with no detectable cadmium (i.e. ca < 2% cadmium), rather than a stoichiometric Sn:Cd oxide. Copyright © 2006 John Wiley & Sons, Ltd.     

Coordination properties of 4(5)-hydroxymethylimidazole and 4(5)-hydroxymethyl-5(4)-methylimidazole towards cobalt(II) ions

Two new complexes of imidazole alcohols, 4-hydroxymethylimidazole (4-CH₂OHim) and 4-hydroxymethyl-5-methylimidazole (4-CH₂OH-5-CH₃im), with cobalt(II) of formula [CoL₂(H₂O)₂](NO₃)₂ were obtained. These compounds were described through single X-ray diffraction studies, spectroscopic (Ir. Far-IR, UV-Vis-NIR) and magnetic measurements. In the present complexes imidazole ligands are bidentate coordinating the heterocyclic ring through pyridine-like nitrogen and the oxygen atom of the hydroxymethyl group (chromophore CoN₂O₄). The shape of Co(II) coordination polyhedra is that of a distorted octahedron, with the equatorial plane defined by the 4-CH₂OHim (or 4-CH₂OH-5-CH₃im) bidentate ligands and two water molecules occupying axial positions (i.e. trans to each other). Formation of successive cobalt(II) complexes with 4-CH₂OH-5-CH₃im in aqueous solution was followed quantitatively by potentiometry.     

SYNTHESIS AND CHARACTERIZATION OF TRIS(ALKYLISOCYANIDE) BIS(TRIARYL-PHOSPHINE)COBALT(II) COMPLEXES

Abstract

A series of complexes having the general formula, [Co(CNR)₃(PR₃)₂]X₂, X = ClO₄, BF₄ with CNR = CNCMe₃, CNCHMe₂, CNC₆H₁₁. CNCH₂Ph and PR₃ = PPh₃, P(C₆H₄Me-p)₃, P(C₆H₄OMe-p)₃ has been synthesized and characterized. Synthesis can be achieved by reaction of [Co(CNR)₄(AsPh₃)₂]X₂ complexes with controlled excess of PR₃ ligands, and by AgClO₄/AgBF₄ oxidation of the [Co(CNR)₃(PR₃)₂]X complexes. The latter procedure is preferable. Alternate syntheses of the [Co(CNR)₃(PR₃)₂]X complexes have also been employed. Five-coordinate Co(II) complexes have not been obtained using CNCMe₃ with P(C₆H₄Me-p)₃ ligands, CNCH₂Ph with P(C₆H₄OMe-p)₃ ligands, or CNC₄H_9-n with PPh₃ ligands. [Co(CNC-Me₃)₃{P(C₆H₄Cl-p)₃}₂]ClO₄ produced only [Co{CNCMe₃)₄H₂O](ClO₄)₂ upon forced oxidation with excess AgClO₄. [Co(CNR)₃(PR₃)₂]X₂ complexes appear to undergo varying degrees of distortion from regular (i.e., D _3h symmetry) axially-disubstituted trigonal bipyramidal coordination in the solid state, as evidenced by v(-N°C) IR patterns, but to assume regular trigonal bipyramidal coordination in solution. Effective magnetic moments indicate one-electron paramagnetism, and solution electronic spectra are compatible with trigonal bipyramidal coordination.     

Spectral and magnetic studies on normal cobalt(II) planar and cobalt(III) octahedral, spin-crossover cobalt(III) octahedral and planar-tetrahedral cobalt(II) carbodithioates

Five cobalt(II) complexes, a normal complex Co(4-PPipzcdt)₂ (4-PPipzcdt = 4-phenylpiperazine-1-carbodithioate), and four zwitterionic complexes, Co(4-PPipzcdtH)₂X₂ and Co(4-MPipzcdtH)₂X₂ (X = Cl, Br; 4-PPipzcdtH = 4-phenylpiperazine-1-carbodithioic acid, 4-MPipzcdtH = 4-methylpiperazine-1-carbodithioic acid), have been synthesized. Normal cobalt(III) complexes of the type Co(4-MPipzcdt)₃ and Co₂ {2-MPipz(cdt)₂}₃ (2-MPipz(cdt)₂ = 2-methylpiperazine-1,4-dicarbodithioate) and two zwitterionic cobalt(III) complexes of the type Co(4-MPipzcdtH)₃X₃ (X = Cl, Br) have also been obtained. In addition to the room temperature IR and electronic spectra and magnetic susceptibility studies, all the complexes, except the normal Co(4-MPipzcdt)₃ and Co(4-PPipzcdt)₂ and zwitterionic Co(4-MPipzcdtH)₃Cl₃, have been investigated by variable-temperature magnetic susceptibility measurements. The results of the variable-temperature magnetic susceptibility studies suggest that two cobalt(II) carbodithioates exhibit a square planar-tetrahedral equilibrium, while two cobalt(III) octahedral carbodithioates show a spin-crossover phenomenon.     

Synthese der Stannatetraphospholane (tBuP)4SnR2 (R = tBu,nBu, C6H5) und (tBuP)4Sn(Cl)nBu Molekül- und Kristallstruktur von (tBuP)4Sn(tBu)2

Synthesis of the Stannatetraphospholanes (tBuP)₄SnR₂ (R = tBu, nBu, C₆H₅) and (tBuP)₄Sn(Cl)nBu Molecular and Crystal Structure of (tBuP)₄Sn(tBu)₂ The reaction of the diphosphide K₂[tBuP-(tBuP)₂-PtBu] 4 with the halogenostannanes (tBu)₂SnCl₂, (nBu)₂SnCl₂, (C₆H₅)₂SnCl₂ or nBuSnCl₃ in a molar ratio of 1 : 1 leads via a [4 + 1]-cyclocondensation reaction to the stannatetraphospholanes (tBuP)₄SnR₂ 3 b–3 d and (tBuP)₄Sn(Cl)nBu 3 e , respectively, with the binary 5-membered P₄Sn ring system. 3 b was characterized by a single crystal structure analysis; the 5-membered ring exists in a planar conformation. The compounds 3 b–3 e were identified by NMR and also by mass spectroscopy; the ³¹P{¹H}-NMR spectra of 3 b–3 d showed an AA′MM′ (AA′MM′X), 3 e on the other hand an ABCD (ABCDX) spin system.     

Synthese und Kristallstrukturen der Acetonitril-,,Addukte“ von Tetraphenylphosphonium-tetrachloro-terbat(III) und -dysprosat(III), (Ph4P)TbCl4(CH3CN) und (Ph4P)DyCl4(CH3CN)

Synthesis and Crystal Structures of the Acetonitrile “Adducts” of Tetraphenylphosphonium Tetrachloroterbate(III) and -dysprosate(III), (Ph₄P)TbCl₄(CH₃CN) and (Ph₄P)DyCl₄(CH₃CN) Single crystals of (Ph₄P)TbCl₄(CH₃CN) ( 1 ) and (Ph₄P)DyCl₄(CH₃CN) ( 2 ) are obtained from the reaction of TbCl₃ and DyCl₃, respectively, with tetraphenylphosphonium chloride in acetonitrile. The crystal structures [monoclinic, P2₁/n (Nr. 14), Z = 4, a = 1065.5(4)/997.3(5) ( 1/2 ); b = 2160.4(5)/1835.8(7); c = 1232.7(3)/1626.7(5) pm, β = 98.82(3)/104.67(4)°; R₁ = 0.0463/0.0469, wR₂ = 0.1051/0.0971 for I > 2σ(I)] contain the dimeric anions [M₂(μ₂-Cl)₂(μ₁-Cl)₆(CH₃CN)₂]^2– (M = Tb, Dy) and (Ph₄P)⁺ cations in slightly different packing modes.     

Trimethylphosphine complexes of tungsten(O) and (IV). X-ray crystal structures of trimethylphosphine tris (phenylacetylene) tungsten(O); bis(trimethylphosphine) tetrakis (methylisocyanide) tungsten(O), and oxodichlorotris (trimethylphosphine) tungsten (IV)

The reduction of WCl₄(PMe₃)₃ by sodium amalgam in presence of phenylacetylene gives W(PMe₃)(PhCCH)₃ (A). Reduction in presence of methylisocyanide gives W(PMe₃)₂(MeNC)₄ (B), while in presence of excess PMe₃ in tetrahydrofuran under hydrogen, WH₂Cl₂(PMe₃)₄ (C) is formed. The reaction of WCl₂(PMe₃)₄ with methanol in tetrahydrofuran gives mixtures of WH₂Cl₂(PMe₃)₄ and WOC1₂(PMe₃)₃ (D).The structures of A, B, and D have been determined by X-ray diffraction.     

Synthese und Struktur der Platin(O)-Verbindungen [(dipb)Pt]2(COD) und (dipb)3Pt2 sowie des clusters Hg6[Pt(dipb)]4 (dipb = (i-Pr)2P(CH2)4P(i-Pr)2)

Synthesis and Structure of the Platinum(0) Compounds [(dipb)Pt]₂(COD) and (dipb)₃Pt₂ and of the Cluster Hg₆[Pt(dipb)]₄ (dipb = (i-Pr)₂P(CH₂)₄P(i-Pr)₂) The reduction of (dipb)PtCl₂ with Na/Hg yields (dipb)Pt as an intermediate which reacts with the amalgam to form the cluster Hg₆[Pt(dipb)]₄ ( 3 ) or decomposes to (dipb)₃Pt₂ ( 2 ) and Pt. In the presence of COD [(dipb)Pt]₂(COD) ( 1 ) is obtained. 1 crystallizes monoclinicly in the space group P2₁/c with a = 1596.1(4), b = 996.5(2), c = 1550.4(3) pm, β = 113.65(2)°, Z = 2. In the dinuclear complex two (dipb)Pt units are bridged by a 1,2-η²-5,6-η² bonded COD ligand. Whereby the C = C double bonds are lengthened to 145 pm. 2 forms triclinic crystals with the space group P1 and a = 1002.0(2), b = 1635.9(3), c = 868.2(2) pm, α = 94.70(2)°, β = 94.45(2)°, σ = 87.95(1)°, Z = 1. In 2 two (dipb)Pt moieties are connected by a μ-dipb ligand in a centrosymmetrical arrangement. 3 is monoclinic with the space group C2/c and a = 1273.8(3), b = 4869.2(6), c = 1660.2(3) pm, β = 95.16(2)°, Z = 4. The clusters Hg₆[Pt(dipb)]₄ have the symmetry C₂. Central unit is a Hg₆ octahedron of which four faces are occupied by Pt(dipb) groups. The bonding in the cluster is discussed on the basis of eight Pt? Hg two center bonds of 267.6 pm and two Pt? Hg? Pt three center bonds with Pt? Hg = 288.0 pm.     

Mesoionic Dithiolates (MIDts) Derived from 1,3-Imidazole-Based Anionic Dicarbenes (ADCs)

Mesoionic dithiolates [(MIDt^Ar)Li(LiBr)₂(THF)₃] (MIDt^Ar={SC(NDipp)}₂CAr; Dipp=2,6-iPr₂C₆H₃; Ar=Ph 3 a , 3-MeC₆H₄ (3-Tol) 3 b , 4-Me₂NC₆H₄ (DMP) 3 c ) and [(MIDt^Ph)Li(THF)₂] ( 4 ) are readily accessible (in≥90 % yields) as crystalline solids on treatments of anionic dicarbenes Li(ADC^Ar) ( 2 a - c ) (ADC^Ar={C(NDipp)₂}₂CAr) with elemental sulfur. 3 a - c and 4 are monoanionic ditopic ligands with both the sulfur atoms formally negatively charged, while the 1,3-imidazole unit bears a formal positive charge. Treatment of 4 with (L)GeCl₂ (L=1,4-dioxane) affords the germylene (MIDt^Ph)GeCl ( 5 ) featuring a three-coordinated Ge atom. 5 reacts with (L)GeCl₂ to give the Ge−Ge catenation product (MIDt^Ph)GeGeCl₃ ( 6 ). KC₈ reduction of 5 yields the homoleptic germylene (MIDt^Ph)₂Ge ( 7 ). Compounds 3 a - c and 4 – 7 have been characterized by spectroscopic studies and single-crystal X-ray diffraction. The electronic structures of 4 – 7 have been analyzed by DFT calculations.     

Über die Reaktionen von CH2=P(NMe2)3 mit Fe(CO)5, Cr(CO)6 und CS2; Molekülstrukturen von [MeP(NMe2)3][(CO)5CrC(O)CH=P(NMe2)3] und (CO)4Fe=C(OMe)CH=P(NMe2)3

The Reactions of CH₂=P(NMe₂)₃ with Fe(CO)₅, Cr(CO)₆, and CS₂; Molecular Structures of [MeP(NMe₂)₃][(CO)₅CrC(O)CH=P(NMe₂)₃], and (CO)₄Fe=C(OMe)CH=P(NMe₂)₃ The ylide CH₂=P(NMe₂)₃ ( 1 ) reacts with several binary transition metal carbonyls M(CO)_x to produce the corresponding salt like compounds [MeP(NMe₂)₃][(CO)_x–1MC(O)CH=P(NMe₂)₃] (M = Fe ( 3 ), Cr ( 4 )). The related reaction with CS₂ leads to the salt [MeP(NMe₂)₃][SC(S)CH=P(NMe₂)₃] ( 2 ). While 4 is thermally stable, 3 rapidly decomposes at room temperature with formation of [MeP(NMe₂)₃]₂[Fe₂(CO)₈] ( 8 ). Alkylation of 3 (at –50 °C) and 4 with MeSO₃CF₃ produces the related carbene complexes (CO)_x–1M=C(OMe)CH=P(NMe₂)₃ ( 5 ) and ( 6 ); the reaction of 3 with Me₃SiCl results in the formation of the carbene complex (CO)₄Fe=C(OSiMe₃)CH=P(NMe₂)₃ ( 7 ). 4 crystallizes in the space group P2₁2₁2₁ (No. 19) with a = 1111.1(2), b = 1476.1(3), c = 1823.1(4) pm and Z = 4. 5 crystallizes in the space group P2₁/n (No. 14) with a = 1303.6(3), b = 910.5(4), c = 1627.0(4) pm, β = 96.06(2)° and Z = 4. The compounds have been characterized by elemental analyses, NMR (¹H, ¹³C, ³¹P) and IR spectroscopy.     

Tricarbonylrhenium(I) and -technetium(I) complexes with bis(2-pyridyl)phenylphosphine and tris(2-pyridyl)phosphine

(NEt₄)₂[Re(CO)₃Br₃] or (NEt₄)₂[Tc(CO)₃Cl₃] react with bis(2-pyridyl)phenylphosphine (PPhpy₂) or tris(2-pyridyl)phosphine (Ppy₃) under formation of neutral tricarbonyl complexes of the composition [M(CO)₃X(L)] (M = Re, X = Br; M = Tc, X = Cl; L = PPhpy₂ or Ppy₃). In all isolated products, the ligands coordinate solely via two of their nitrogen atoms. All attempts to force a tripodal coordination of the phosphinopyridines failed. Removal of the bromo ligands from (NEt₄)₂[Re(CO)₃Br₃] by the addition of AgNO₃ in THF/water, and subsequent reaction of the resulting [Re(CO)₃(THF)₃](NO₃)with Ppy₃ yielded the complex [Re(CO)₃(NO₃)(Ppy₃-N,N′)] with a monodentate coordinated nitrato ligand. The products have been characterized spectroscopically and by X-ray structure analyses.     

Darstellung und Strukturen von (Et4N)2[Re(CO)3(NCS)3] und (Et4N)[Re(CO)2Br4]

Syntheses and Structures of (Et₄N)₂[Re(CO)₃(NCS)₃] and (Et₄N)[Re(CO)₂Br₄] Rhenium(I) and rhenium(III) carbonyl complexes can easily be prepared by ligand exchange reactions starting from (Et₄N)₂[Re(CO)₃Br₃]. Using nonoxidizing reagents the facial Re^I(CO)₃ unit remains and only the bromo ligands are exchanged. Following this procedure, (Et₄N)₂[Re(CO)₃(NCS)₃] can be obtained in high yield and purity using trimethylsilylisothiocyanate. The compound crystallizes in the monoclinic space group P2₁/n, a = 18.442(5), b = 17.724(3), c = 18.668(5) Å, β = 92.54(1)°, Z = 8. The NCS^? ligands are coordinated via nitrogen. The reaction of [Re(CO)₃Br₃]^2? with Br₂ yields the rhenium(III) anion [Re(CO)₂Br₄]^?. The tetraethylammonium salt of this complex crystallizes in the noncentrosymmetric, orthorhombic space group Cmc2₁, a = 8.311(1), b = 25.480(6), c = 8.624(1) Å, Z = 4. The carbonyl ligands are positioned in a cis arrangement. Their strong trans influence causes a lengthening of the Re? Br bond distances by at least 0.05 Å.     

Synthese und Struktur der Phosphor-verbrückten Übergangsmetallkomplexe [Fe2(CO)6(PR)6] (R = tBu,iPr), [Fe2(CO)4(PiPr)6], [Fe2(CO)3Cl2(PtBu)5], [Co4(CO)10(PiPr)3], [Ni5(CO)10(PiPr)6] und [Ir4(C8H12)4Cl2(PPh)4]

Synthesis and Structure of the Phosphorus-bridged Transition Metal Complexes [Fe₂(CO)₆(PR)₆] (R = ^tBu, ⁱPr), [Fe₂(CO)₄(PⁱPr)₆], [Fe₂(CO)₃Cl₂(P^tBu)₅], [Co₄(CO)₁₀(PⁱPr)₃], [Ni₅(CO)₁₀(PⁱPr)₆], and [Ir₄(C₈H₁₂)₄Cl₂(PPh)₄] (P^tBu)₃ and (PⁱPr)₃ react with [Fe₂(CO)₉] to form the dinuclear complexes [Fe₂(CO)₆(PR)₆] (R = ^tBu: 1 ; ⁱPr: 2 ). 2 is also formed besides [Fe₂(CO)₄(PⁱPr)₆] ( 3 ) in the reaction of [Fe(CO)₅] with (PⁱPr)₃. When PⁱPr(P^tBu)₂ and PⁱPrCl₂ are allowed to react with [Fe₂(CO)₉] it is possible to isolate [Fe₂(CO)₃Cl₂(P^tBu)₅] ( 4 ). The reactions of (PⁱPr)₃ with [Co₂(CO)₈] and [Ni(CO)₄] lead to the tetra- and pentanuclear clusters [Co₄(CO)₁₀(PⁱPr)₃] ( 5 ), [Ni₄(CO)₁₀(PⁱPr)₆] [2] and [Ni₅(CO)₁₀(PⁱPr)₆] ( 6 ). Finally the reaction of [Ir(C₈H₁₂)Cl]₂ with K₂(PPh)₄ leads to the complex [Ir₄(C₈H₁₂)₄Cl₂(PPh)₄] ( 7 ). The structures of 1–7 were obtained by X-ray single crystal structure analysis (1: space group P2₁/c (Nr. 14), Z = 8, a = 1 758.8(16) pm, b = 3 625.6(18) pm, c = 1 202.7(7) pm, β = 90.07(3)°; 2 : space group P1 (Nr. 2), Z = 1, a = 880.0(2) pm, b = 932.3(3) pm, c = 1 073.7(2) pm, α = 79.07(2)°, β = 86.93(2)°, γ = 72.23(2)°; 3 : space group Pbca (Nr. 61), Z = 8, a = 952.6(8) pm, b = 1 787.6(12) pm, c = 3 697.2(30) pm; 4 : space group P2₁/n (Nr. 14), Z = 4, a = 968.0(4) pm, b = 3 362.5(15) pm, c = 1 051.6(3) pm, β = 109.71(2)°; 5 : space group P2₁/n (Nr. 14), Z = 4, a = 1 040.7(5) pm, b = 1 686.0(5) pm, c = 1 567.7(9) pm, β = 93.88(4)°; 6 : space group Pbca (Nr. 61), Z = 8, a = 1 904.1(8) pm, b = 1 959.9(8) pm, c = 2 309.7(9) pm. 7 : space group P1 (Nr. 2), Z = 2, a = 1 374.4(7) pm, b = 1 476.0(8) pm, c = 1 653.2(9) pm, α = 83.87(4)°, β = 88.76(4)°, γ = 88.28(4)°).     

Neue Phosphido-verbrückte Mehrkernkomplexe des Ag,Cd und Zn Die Kristallstrukturen von [Ag4(PPh2)4(PMe3)4], [Ag6(PPh2)6(PtBu3)2] und [M4Cl4(PPh2)4(PnPr3)2] (M = Zn,Cd)

New Phosphido-bridged Multinuclear Complexes of Ag, Cd and Zn. The Crystal Structures of [Ag₄(PPh₂)₄(PMe₃)₄], [Ag₆(PPh₂)₆(P^tBu₃)₂] and [M₄Cl₄(PPh₂)₄(PⁿPr₃)₂] (M = Zn, Cd) AgCl reacts with Ph₂PSiMe₃ in the presence of a tertiary Phosphine PMe₃ or P^tBu₃ to form the multinuclear complexes [Ag₄(PPh₂)₄(PMe₃)₄] ( 1 ) and [Ag₆(PPh₂)₆(P^tBu₃)₂] ( 2 ). In analogy to that MCl₂ reacts with Ph₂PSiMe₃ in the presence of PⁿPr₃ to form the two multinuclear complexes [M₄Cl₄(PPh₂)₄(PⁿPr₃)₂] (M = Zn ( 3 ), Cd ( 4 )). The structures were characterized by X-ray single crystal structure analysis ( 1 : space group Pna2₁ (Nr. 33), Z = 4, a = 1 313.8(11) pm, b = 1 511.1(6) pm, c = 4 126.0(18) pm, 2 : space group P–1 (Nr. 2), Z = 2, a = 1 559.0(4) pm, b = 1 885.9(7) pm, c = 2 112.4(8) pm, α = 104.93(3)°, β = 94.48(3)°, γ = 104.41(3)°; 3 : space group C2/c (Nr. 15), Z = 4, a = 2 228.6(6) pm, b = 1 847.6(6) pm, c = 1 827.3(6) pm, β = 110.86(2); 4 : space group C2/c (Nr. 15), Z = 4, a = 1 894.2(9) pm, b = 1 867.9(7) pm, c = 2 264.8(6) pm, β = 111.77(3)°). 3 and 4 may be considered as intermediates on the route towards polymeric [M(PPh₂)₂]_n (M = Zn, Cd).