Clusteraufbau durch Photolyse von R3PAuN3. VIII. Synthese und Kristallstruktur von [(Ph3PAu)5Mo(CO)4]PF6 · CH2Cl2 und (Ph3PAu)3Co(CO)3

Cluster Synthesis by Photolysis of R₃PAuN₃. VIII. Synthesis and Crystal Structure of [(Ph₃PAu)₅Mo(CO)₄]PF₆ · CH₂Cl₂ and (Ph₃PAu)₃Co(CO)₃ Photolysis of a mixture of Ph₂PAuN₃ and Mo(CO)₆ in THF yields [(Ph₃PAu)₅Mo(CO)₄]⁺ (1), which can be crystallized from CH₂Cl₂/diisopropylether as orange 1 · PF₆ · CH₂Cl₂ with the space group P2₁/c and a = 1681.4(5), b = 2215.6(12), c = 2761.5(9) pm, β = 91.54(3)°, Z = 4. The Au₅Mo center of cluster 1 forms a capped trigonal bipyramid with the Mo atom in equatorial position and almost equal Mo? Au distances between 279.9(5) and 284.6(7) pm to all five Au atoms. The Au? Au distances range from 272.2(4) to 301.3(4) pm. The Mo(CO)₄ group causes three v(C0) at 1975, 1915 and 1890cm^?1. Reaction of Ph₃PAuCo(CO)₄ with Ph₃PAuPF₆ affords the known cluster cation [(Ph₃PAu)₄Co(CO)₃]⁺ in high yield. It can be degraded with C1^? to the neutral cluster (Ph₃PAu)₃Co(CO)₃ (2). 2 forms air stable, yellow crystals with the space group P2₁/n and a = 1359.4(4), b = 2041.0(5), c = 1853.2(6)pm, β = 91.47(1)°, Z = 4. The Au₃Co core of 2 has a tetrahedral structure with distances Co? Au between 250.4(1) and 254.0(2) pm and Au? Au between 279.5(1) and 285.1(1) pm. v(C0) are observed at 1963, 1905 and 1891 cm^?1. Reaction of 2 with [(Ph₃PAu)₄Co(CO)₃]⁺ yields the condensed cluster [(Ph₃PAu)₆AuCo₂(CO)₆]⁺.     

Synthese und Struktur von [(Ph3PAu)6Co(CO)2](PF6) und [(Ph3PAu)7Co(CO)2](PF6)2

Synthesis and Structure of [(Ph₃PAu)₆Co(CO)₂](PF₆) and [(Ph₃PAu)₇Co(CO)₂](PF₆)₂ By the reaction of (Ph₃PAu)₄Co[(CO)₃]⁺ with OH^? in the presence of excess Ph₃PAuCl the larger cluster cations [(Ph₃PAu)₆Co(CO)₂]⁺ ( 1 ) and [(Ph₃PAu)₇Co(CO)₂]²⁺ ( 2 ) can be built up with 1 being the main product. 1 crystallizes with PF^?₆ as counterion in the monoclinic space group C2/c with a = 3008.3(6); b = 1339.1(2); c = 2909.4(6) pm; β = 103.08(1)°; Z = 4. The inner core of the cluster cation 1 with the symmetry C₂ has the form of a bicapped trigonal bipyramid with the heteroatom in equatorial position, and distances Au? Au between 280.4(1) and 288.4(1) pm and Co? Au between 254.9(1) and 257.1(2) pm. 2 · (PF₆)₂ crystallizes in the triclinic space group P1 with a = 2155.7(1); b = 1720.6(1); c = 3543.6(1) pm; α = 91.89(1)°; β = 97.51(1); γ = 89.92(1)°; Z = 4. The unit cell contains two symmetry independent cluster cations 2 of about the same geometry. The cluster skeleton Au₇Co can be described as fragment of an icosahedron formed by seven gold atoms with the Co atom in its center. The Au? Au distances range from 274.8(3) to 332.6(3) pm, and the Co? Au distances are 256.8(6) to 264.7(5) pm. The bonding in 1 and 2 is discussed.     

Clusteraufbau durch Photolyse von Azidokomplexen des Platins und Golds. Synthesen und Kristallstrukturen von [(Ph3PAu)6(AuCl)3Pt(CO)], [(dppe)PtCo2(CO)7] und [(Ph3PAu)4Pt(dppe)](PF6)2

Cluster Synthesis by Photolysis of Azido Complexes of Platinum and Gold. Syntheses and Crystal Structures of [(Ph₃PAu)₆(AuCl)₃Pt(CO)], [(dppe)PtCo₂(CO)₇] and [(Ph₃PAu)₄Pt(dppe)](PF₆)₂ Photolysis of a mixture of Ph₃PAuN₃, Ph₃PAuCl and (Ph₃P)₂Pt(N₃)₂ in THF yields after chromatographic separation with CH₂Cl₂/EtOH as eluens the cluster [(Ph₃PAu)₆(AuCl)₃Pt(CO)] ( 1 ). It crystallizes in the triclinic space group P1 with the lattice parameters a = 2 139.3(4), b = 2 457.1(4), c = 2 561.9(1) pm, α = 79.74(9)°, β = 80.06(6)°, γ = 66.05(5)°, Z = 4. The nine gold atoms form a fragment of an icosahedron with the platinum atom in its center. Upon photolysis of (dppe)Pt(N₃)₂ with Co₂(CO)₈ in THF one m?₂-CO ligand of the cobalt carbonyl is substituted by a (dppe)Pt group. The resulting cluster [(dppe)PtCo₂(CO)₇] ( 2 ) crystallizes monoclinically in the space group P2₁/n with a = 1 303.9(3), b = 1 768.1(8), c = 1 461.4(4) pm, β = 102.81(1)°, Z = 4. Photolysis of 2 with excess Ph₃PAuN₃ affords the clusters [(Ph₃PAu)₄Pt(dppe)]²⁺ ( 3 ), and [(Ph₃PAu)₆AuCo₂(CO)₆]⁺. 3 crystallizes with PF as counterions in the triclinic space group P1 with a = 1 369.1(4), b = 1 505.0(4), c = 2 773.0(8) pm, α = 84.74(1)°, β = 87.37(2)°, γ = 65.94(2)°, Z = 2. The Au₄Pt skeleton of 3 forms a trigonal bipyramid with the platinum atom in equatorial position.     

Synthese und Struktur von (Ph3PAu)3Mn(CO)4

Synthesis and Structure of (Ph₃PAu)₃Mn(CO)₄ Photolysis of (Ph₃PAu)Mn(CO)₅, Ph₃PAuN₃ and Ph₃PAuNCO yields (Ph₃PAu)₃Mn(CO)₄ ( 1 ). 1 crystallizes in the monoclinic space group P2₁/n with a = 1 031.3(1); b = 3 095.2(3), c = 3 386.3(3) pm; β = 97.58(3)°; Z = 8. The crystal structure contains two symmetry independent clusters 1 of the same geometry. Their inner core MnAu₃ forms a rhombus with distances Mn? Au of about the same lengths between 258.4(4) and 262.0(4) pm. The distances Au? Au range from 276.6(2) to 281.3(2) pm. The bonding in 1 is discussed and compared with those of (Ph₃PAu)₃Co(CO)₃ having the same total number of electrons but a tetrahedral framework.     

Darstellung und Kristallstrukturen von Dicyanamido(triphenylphosphan)gold(I) und Nitrosodicyanmethanido(triphenylphosphan)gold(I)

Preparation and Crystal Structures of Dicyanamido(triphenylphosphane)gold(I) and Nitrosodicyanomethanido(triphenylphosphane)gold(I) The coordination compounds [(Ph₃P)Au{N(CN)₂}] ( 1 ) and [(Ph₃P)Au{ONC(CN)₂}] ( 2 ) are obtained by the reaction of [Au(PPh₃)]NO₃ with Na[N(CN)₂] or K[ONC(CN)₂] in CH₂Cl₂. The compounds are characterized by IR spectroscopy and by crystal structure determination. 1 crystallizes triclinic in the space group P 1 with a = 930.16(4), b = 1011.89(13), c = 1118.35(16) pm, α = 115.327(10), β = 90.899(8), γ = 103.394(8)°, Z = 2. 2 crystallizes monoclinic in the space group P2₁/n with a = 832.59(10), b = 1139.30(16), c = 2078.9(4) pm, β = 99.84(2)°, Z = 4. The crystal structures of both compounds are built up by pairs of antiparallel oriented molecules with linear coordinated gold atoms and weak intermolecular Au–N‐interactions.     

Preparation and Characterization of a Novel Palladium Complex: cis‐Dichloride(1,2‐bis(diphenylphosphino)vinyl‐P,P′,C)palladium(II)‐(bis(diphenylphosphino)methane‐P,P′)cobaltacarbonyl

A novel palladium complex 4, cis‐dichloride(1,2‐bis(diphenylphosphino)vinyl‐P,P′,C)palladium(II)‐(bis(diphenylphosphino)methane‐P,P′)cobaltacarbonyl, was obtained and characterized from the treatment of [(μ‐Ph₂PCH₂PPh₂)Co₂(CO)₄][(Ph₂PC≡CPPh₂)‐PdCl₂] 3 with hydrochloric acid. The framework of 4 can be regarded as a grouping of two metal‐containing fragments: ‐Co(CO)₂(dppm) and PdCl2(μ‐P,P‐Ph₂PCH=C(‐)PPh₂).     

Zur Reaktion von Metall-koordinierten Kohlenmonoxid mit Yliden XXII. Bis(diphenylphosphino)methanid-Eisen-Komplexe Cp(L)Fe(Ph2PCHPPh2) (L = CO,Me3P)

The reaction of [Cp(CO)(dppm)Fe]BF₄ (1a) with the phosphorus ylide Me₃PCH₂ yields the novel bis(phosphino)methanideiron complex Cp(CO)Fe(Ph₂PCHPPh₂) (2), which upon photolysis in the presnece of Me₃P is converted into Cp(Me₃P)Fe(Ph₂PCHPPh₂ (3). Reaction of 2 with MeOSO₂CF₃ gives a mixture of the iron salts [(Cp(CO)Fe(Ph₂PCR(R′)PPh₂)]CF₃SO₃ (R = R′ = H (1b), R = R′ = Me (6) and R = H, R′ = Me (syn/anti-4)).     

Chemie polyfunktioneller Moleküle. 97. Beiträge zur Komplexchemie des Lithium-bis(diphenylphosphino)amids,des Bis(diphenylphosphino)amins und des Tris(diphenylphosphino)amins

Chemistry of Polyfunctional Molecules. 97. Contributions to the Coordination Chemistry of Lithium-bis(diphenylphosphino)amide, Bis(diphenylphosphino)amine, and Tris(diphenyl-phosphino)amine (Ph₂P)₂NLi ( 1 ) forms with AuCl(PPh₃) the already known complex [Au(Ph₂P)₂N]₂ ( 2 ), which now has been proved by mass spectroscopy to possess the postulated dimeric structure. 2 gives with HCl, HClO₄, and HBF₄ the new compounds [ClAu(Ph₂P)₂NH]₂ ( 3a ) and [Au(Ph₂P)₂NH…?X]₂ [X = ClO₄ ( 3b ), BF₄ ( 3c )]. In analogy the neutral complex Fe(C₅H₅)(CO)(Ph₂P)₂N ( 5 ) os obtained from FeCl(C₅H₅)(CO)₂ and 1. 5 reacts with HCl to [Fe(C₅H₅)(CO)(Ph₂P)₂NH…?Cl] ( 6a ). The last one can also be prepared by direct reaction of FeCl(C₅H₅)(CO)₂ with (Ph₂P)₂NH ( 4 ). In the same way FeBr(C₅H₅)(CO)₂ reacts with 4 yielding [Fe(C₅H₅)(CO)(Ph₂P)₂NH…?Br] ( 6b ), which leads under metathesis with NH₄PF₆ to [Fe(C₅H₅)(CO)(Ph₂P)₂NH]PF₆ ( 6c ). With PdCl₂(NCPh)₂ the ligand 1 forms Pd[(Ph₂P)₂N]₂ ( 7 ), which also can be synthesized in another way, but is now for the first time characterized in a spectroscopically detailed manner. Cr(CO)₄(Ph₂P)₂NPPh₂ reacts with AuCl(CO) to Cr(CO)₄(Ph₂P)₂NPPh₂AuCl ( 8 ). This compound gives with Cr(CO)₄(Ph₂P)₂NLi the trimetallic complex (OC)₄Cr(Ph₂P)₂NPPh₂AuN(PPh₂)₂Cr(CO)₄ ( 9 ). (Ph₂P)₃N ( 10 ) yields with AuCl(CO) in the molar ratio of 1:3 the compound [ClAuPh₂P]₃N ( 11 ).     

Synthese und Kristallstruktur von (C5H5)Mo(CO)3(AuPPh3) und [(C5H5)Mo(CO)2(AuPPh3)4]PF6

Synthesis and Crystal Structure of (C₅H₅)Mo(CO)₃(AuPPh₃) and [(C₅H₅)Mo(CO)₂(AuPPh₃)₄]PF₆ CpMo(CO)₃(AuPPh₃) is obtained by the reaction of Li[CpMo(CO)₃] with Ph₃PAuCl at ?95°C in CH₂Cl₂. It crystallizes in the monoclinic space group C2/c with a = 2625.1(7), b = 883.2(1), c = 2328.4(7) pm, β = 116.39(1)° und Z = 8. In the complex the AuPPh₃ group is coordinated to the CpMo(CO)₃ fragment with a Au? Mo bond of 271,0 pm. The Mo atom thus achieves a square pyramidal coordination with the center of the Cp ring in apical position. CpMo(CO)₃(AuPPh₃) reacts under uv irradiation with an excess of Ph₃PAuN₃ to afford the cluster cation [CpMo(CO)₂(AuPPh₃)₄]⁺. It crystallizes as [CpMo(CO)₂(AuPPh₃)₄]PF₆ · 2 CH₂Cl₂ in the orthorhombic space group P2₁2₁2₁ with a = 1553.9(1), b = 1793.8(2), c = 2809.8(7) pm und Z = 4. The five metal atoms form a trigonal bipyramidal cluster skeleton with the Mo atom in equatorial position. The Mo? Au distances range from 275.5 to 280.8 pm, and the Au? Au distances are between 281.2 and 285.6 pm.     

THE REACTIONS OF [MoCl(GeCl3)(CO)3(NCMe)2] WITH NEUTRAL BI- AND TERDENTATE DONOR LIGANDS

Abstract

The reaction of [MoCl(GeCl₃)(CO)₃(NCMe)₂] with an equimolar quantity of L?L {L?L = 2,2′-bipy, 1,10-phen, Ph₂P(CH₂)_nPPh₂ (n = 1 or 2)} in CH₂Cl₂ at room temperature gave either [MoCl(GeCl₃)(CO)₃(L?L)] (L?L = 2,2′-bipy or 1,10-phen) (1 and 2) or [MoCl(GeCl₃)(CO)₂ (NCMe)(L?L)]{L?L = Ph₂P(CH₂)_nPPh₂ (n = 1 or 2) (3 or 4), respectively. Equimolar quantities of [MoCl(GeCl₃)(CO)₂(NCMe){Ph₂P(CH₂)PPh₂}] (3) and L?L {L?L = 2,2′-bipy or Ph₂P(CH)₂PPh₂} react in CH₂Cl₂ at room temperature to afford the cationic complexes [Mo(GeCl₃)(CO)₂{Ph₂P(CH₂) PPh₂}(L?L)]Cl (5 and 6) in good yield. The cationic nature of 6 was established by chloride exchange by reacting Na[BPh₄] with 6 in acetonitrile to give the tetraphenylborate complex [Mo(GeCl₃)(CO)₂{Ph₂P(CH₂)PPh₂}₂][BPh₄] (7). Reaction of equimolar quantities of [MoCl(GeCl₃) (CO)₃(NCMe)₂] and PhP(CH₂CH₂PPh₂)₂ in CH₂Cl₂ at room temperature afforded the dicarbonyl complex [MoCl(GeCl₃)(CO)₂{PhP(CH₂CH₂PPh₂)₂}] (8) in good yield.     

Novel Cyclometallated Complexes Derived From a Halogenated Thiosemicarbazone. Crystal and Molecular Structures of 2‐FC6H4C(Me)=NN(H)C(=S)NHPh and [(Pd{2‐FC6H3C(Me)=NN=C(S)NHPh})2(μ‐PPh2(CH2)2PPh2)]

Treatment of the thiosemicarbazone 2‐FC₆H₄C(Me)=NN(H)C(=S)NHPh, a , with palladium(II) acetate in acetic acid, or with lithium tetrachloropalladate(II) in methanol, gave the tetranuclear cyclometallated complex [Pd{2‐FC₆H₃C(Me)=NN=C(S)NHPh}]₄ (1a) . Reaction of 1a with the diphosphines Ph₂P(CH₂)₂PPh₂ (dppe), Ph₂PCH=CHPPh₂ (trans‐dpe) Ph₂P(CH₂)₃Ph₂ (dppp) or Ph₂P(CH₂)₄Ph₂ (dppb) in a 1:2 molar ratio gave the dinuclear cyclometallated complexes [(Pd{2‐FC₆H₃C(Me)=NN=C(S)NHPh})₂(μ‐Ph₂P(CH₂)_nPPh₂)], (n = 2, 2a ; 3, 4a ; 4, 5a ) and [(Pd{2‐FC₆H₃C(Me)=NN=C(S)NHPh})₂(μ‐Ph₂PCH=CHPPh₂)], ( 3a ). The X‐ray crystal structure of ligand a and of complex 2a are described. The structure of complex 2a shows the palladium atom is bonded to four different donor atoms: C, N, S and P.     

Cluster chemistry: XXIII. Mono-, di- and tri-auration of H4Ru4(CO)12 with [{Au(PPh3)}3O][BF4]: X-ray crystal structure of HRu4Au3(CO)12(PPh3)3

Reactions between [H₃Ru₄(CO)₁₂]^? and [{Au(PPh₃)}₃O]⁺ afford H₃Ru₄-Au(CO)₁₂(PPh₃), H₂Ru₄Au₂(CO)₁₂(PPh₃)₂ and HRu₄Au₃(CO)₁₂(PPh₃)₃. The X-ray structure of the latter shows that it has the unusual bicapped trigonal bipyramidal metal core, in which two Ru₂Au faces of the Ru₄Au fragment are capped by the other two Au atoms. The central Au atom is asymmetrically attached to the Ru₃ face as a result of the interaction of a phenyl ring of the PPh₃ ligand with two of the CO groups. Metal-metal separations are: two Au-Au, 2.837(1) Å; Ru-Ru, six between 2.805–3.004(3) Å; Au-Ru, seven between 2.821–3.007(2) Å. HRu₄Au₃(CO)₁₂(PPh₃)₃ is monoclinic, space group P2₁/n, with a 18.754(3), b 18.459(5), c 22.317(4) Å, β 113.06(2)°; 2852 data [I > 2.5σ(I)] were refined to R, R_w 0.038, 0.038.     

Synthese und Struktur chiraler Heterometallatetrahedrane des Typs [Re2(M1PPh3)(M2PPh3)(μ‐PCy2)(CO)7C≡CPh] (M1 = Ag,Au; M2 = Cu,Ag, Au)

Syntheses and Structure of Chiral Metallatetrahedron Complexes of the Type [Re₂(M¹PPh₃)(M²PPh₃)(μ‐PCy₂)(CO)₇C≡CPh] (M¹ = Ag, Au; M² = Cu, Ag, Au) From the reaction of Li[Re₂(μ‐H)(μ‐PCy₂)(CO)₇(C(Ph)O)] ( 1 ) with Ph₃AuC≡CPh both benzaldehyde and the trinuclear complex Li[Re₂(AuPPh₃)(μ‐PCy₂)(CO)₇C≡CPh] ( 2a ) were obtained in high yield. The complex anion was isolated as its PPh₄‐salt 2b . The latter reacts with coinage metal complexes PPh₃M²Cl [M² = Cu, Ag, Au] to give chiral heterometallatetrahedranes of the general formula [Re₂(AuPPh₃)(M²PPh₃)(μ‐PCy₂)(CO)₇C≡CPh] (M² = Cu 3a , Ag 3b , Au 3c ). The corresponding complex [Re₂(AgPPh₃)₂(μ‐PCy₂)(CO)₇C≡CPh] ( 3d ) is obtained from the reaction of [Re₂(AgPPh₃)₂(μ‐PCy₂)(CO)₇Cl] ( 4 ) with LiC≡CPh. 3d undergoes a metathesis reaction in the presence of PPh₃CuCl giving [Re₂(AgPPh₃)(CuPPh₃)(μ‐PCy₂)(CO)₇C≡CPh] ( 3e ) and PPh₃AgCl. Analogous metathesis reactions are observed when 3c is reacted with PPh₃AgCl or PPh₃CuCl giving 3a or 3b , respectively. The reaction of 1 with PPh₃AuCl gives benzaldehyde and Li[Re₂(AuPPh₃)(μ‐PCy₂)(CO)₇Cl] ( 5a ) which upon reaction with PhLi forms the trinuclear complex Li[Re₂(AuPPh₃)(μ‐PCy₂)(CO)₇Ph] ( 6a ). Again this complex was isolated as its PPh₄‐salt 6b . In contrast to 2b , 6b reacts with one equivalent of Ph₃PAuCl by transmetalation to give Ph₃PAuPh and PPh₄[Re₂(AuPPh₃)(μ‐PCy₂)(CO)₇Cl] ( 5b ). The X‐ray structures of the compounds 3a , 3b , 3e and 4 are reported.     

Cluster synthesis by photolysis of R3PAuN3 IV. Synthesis and structure of [(Ph3PAu)4Mn(CO)4]PF6

Photolysis of R₃PAuN₃ in the presence of Mn₂(CO)₁₀ yields the cationic cluster compounds [(Ph₃PAu)₄Mn(CO)₄]⁺ (1) and [(Ph₃PAu)₆Mn(CO)₃]⁺ (2), which can be separated by column chromatography. Compound 1 crystallizes from CH₂Cl₂-diisopropylether after addition of PF₆⁻ as 1 · PF₆· 0.5CH₂Cl₂ in the triclinic space group P1̄ with a = 1709.8(6) pm, b = 2017.3(7) pm, c = 1180.3(7) pm, α = 106.42(3)°, β = 98.81(4)°, γ = 102.82(4)°, V = 3704.9 × 10⁶ pm³, Z = 2. The central unit of 1 is a trigonal bipyramid Au₄Mn with the manganese atom in equatorial position. The AuAu distances are in the range 277.3 to 292.2 pm. The manganese atom forms two short bonds of 263.3 and 264.0 pm to the axial gold atoms and two longer bonds of 272.3 and 273.3 pm to the equatorial neighbors. A d²sp³ hybridization can be assumed for the manganese atom. Four of the orbitals are used for the MnCO σ-bonds. The remaining two are then pointing approximately to the center of the Au₃ triangular faces.     

On the Reaction of [(CO)3Fe(μ‐Me2NCO)2Fe(CO)2(NHMe2)] with Chelating Ligands — X‐Ray Structures of New Binuclear μ‐Carbamoyl Complexes

Reaction of the binuclear μ‐carbamoyl complex [(CO)₃Fe(μ‐Me₂NCO)₂Fe(CO)₂(HNMe₂)] ( 1 ) in toluene with the chelating ligands Ph₂PCH₂PPh₂ (dppm) and Ph₂PCH₂CH₂PPh₂ (dppe) gives different results. With dppm only the complex [(CO)₃Fe(μ‐Me₂NCO)₂Fe(CO)₂(dppm)] ( 3 ) with a dangling ligand is obtained under replacement of amine, whereas with dppe depending on the reaction conditions up to three compounds are found. A 1 : 1 mixture of the educts generates the related complex [(CO)₃Fe(μ‐Me₂NCO)₂Fe(CO)₂(dppe)] ( 4 ) together with the tetranuclear complex [{(CO)₃Fe(μ‐Me₂NCO)₂Fe(CO)₂}₂(dppe)] (5 ). 4 slowly converts into [(CO)₃Fe(μ‐Me₂NCO)₂Fe(CO)(dppe)] ( 6 ) with dppe acting as a chelating ligand. 6 is the first compound in this series in which one of the five CO groups is replaced by another donor. A 2 : 1 molar ratio of 1 and dppe quantitatively produces 5 . Addition of CO to a solution of 6 proceeds under slow reversible conversion of the complex into 4 . The compounds were characterized by the usual spectroscopic methods; 3 , 5 and 6 were also studied by X‐ray diffraction analyses.     

Platinum,iridium and rhodium complexes with substituted bis-(diphenylphosphino)methane ligands Ph2PCH(R)PPh2 (R = Me,Ph or SiMe3)

Substituted phosphines of the type Ph₂PCH(R)PPh₂ and their Pt^II complexes [PtX₂{Ph₂PCH(R)PPh₂}] (R = Me, Ph or SiMe₃; X = halide) were prepared. Treatment of [PtCl₂(NCBu^t)₂] with Ph₂PCH(SiMe₃)-PPh₂ gave [PtCl₂(Ph₂PCH₂PPh₂)], while treatment with Ph₂PCH(Ph)PPh₂ gave [Pt{Ph₂PCH(Ph)PPh₂}₂]Cl₂. Reaction of p-MeC₆H₄C≡CLi or PhC≡CLi with [PtX₂{Ph₂PCH(Me)PPh₂}] gave [Pt(C≡CC₆H₄Me-p)₂-{Ph₂PCH(Me)PPh₂}] (X = I) and [Pt{Ph₂PC(Me)PPh₂}₂](X = Cl),while reaction of p-MeC₆H₄C≡CLi with [Pt{Ph₂PCH(Ph)PPh₂}₂]Cl₂ gave [Pt{Ph₂PC(Ph)PPh₂}₂]. The platinum complexes [PtMe₂(dpmMe)] or [Pt(CH₂)₄(dpmMe)] fail to undergo ring-opening on treatment with one equivalent of dpmMe [dpmMe = Ph₂PCH(Me)PPh₂]. Treatment of [Ir(CO)Cl(PPh₃)₂] with two equivalents of dpmMe gave [Ir(CO)(dpmMe)₂]Cl. The PF₆ salt was also prepared. Treatment of [Ir(CO)(dpmMe)₂]Cl with [Cu(C≡CPh)₂], [AgCl(PPh₃)] or [AuCl(PPh₃)] failed to give heterobimetallic complexes. Attempts to prepare the dinuclear rhodium complex [Rh₂(CO)₃(μ-Cl)(dpmMe)₂]BPh₄ using a procedure similar to that employed for an analogous dpm (dpm = Ph₂PCH₂PPh₂) complex were unsuccessful. Instead, the mononuclear complex [Rh(CO)(dpmMe)₂]BPh₄ was obtained. The corresponding chloride and PF₆ salts were also prepared. Attempts to prepare [Rh(CO)(dpmMe)₂]Cl in CHCl₃ gave [RhHCl(dpmMe)₂]Cl. Recrystallization of [Rh(CO)(dpmMe)₂]BPh₄ from CHCl₃/EtOH gave [RhO₂(dpmMe)₂]BPh₄. Treatment of [Rh(CO)₂Cl₂]₂ with one equivalent of dpmMe per Rh atom gave two compounds, [Rh(CO)(dpmMe)₂]Cl and a dinuclear complex that undergoes exchange at room temperature between two formulae: [Rh₂(CO)₂(μ-Cl)(μ-CO)(dpmMe)₂]Cl and [Rh₂(CO)₂-(μ-Cl)(dpmMe)₂]Cl. This revised version was published online in June 2006 with corrections to the Cover Date.     

The Syntheses and Crystal Structures of cis-[Bis(diphenylphosphino)methane][1,2-bis(diphenylphosphlno)ethane] dicarbonylmolybdenum(O) and cis-[1,2-Bis(diphenylphosphino)ethane] [cis-1,2-bis(diphenylphosphino) ethylene]dicarbonylmolybdenum(0)

The title compounds, Mo(CO)₂(Ph₂PCH₂PPh₂)(Ph₂PCH₂CH₂PPh₂), Mo(CO)₂(dppm)(dppe) 1, and Mo(CO)₂(Ph₂PCH₂CH₂PPh₂)(Ph₂PCH = CHPPh₂), Mo(CO)₂(dppe)(cis-vpp) 2, were prepared from Mo(CO)₆ and the corresponding bidentate diphosphine ligands in n-decane under nitrogen atomosphere. Crystals of 1 are monoclinic, space group P 2₁/c, with a = 19.072(3), b = 11.348(3), c = 23.57(1) Å, β = 99.64(3)°, Z = 4, and the final residual R(F) = 0.044 for 4810 observed reflections; data of 2 are triclinic, space group P 1, with a = 12.091(3), b = 12.186(8), c = 18.934(5) Å, α = 96.93(4),β = 108.15(2), γ = 107.08(4)deg;, Z = 2, and the final residual R(F) = 0.058 for 4570 observed reflections. The distortion of compound 1 is more pronounced than that of compound 2, The two Mo-P lengths in the same bidentate chelate ligand for both compounds are different. Among them, the two larger Mo-P bond lengths for compound 2 are similar, but significantly different for 1.     

Gold(I) and Palladium(II) Complexes Containing the Functionalized Ylides Triarylphosphonium Cyanomethylide or 2-Cyanoethylide (R3P=CHR′, R′=CN,CH2CN)

The coordination properties of ylides R₃P=CHCN and R₃P=CHCH₂CN were studied. Ylide R₃P=CHCN reacts with [AuCl(tht)] (molar ratio 1 : 1, tht=tetrahydrothiophene) to give [AuCl{CH(PPh₃)CN}] ( 1 ). Dinuclear complexes [(AuL)₂{μ-C(PR₃)CN}]ClO₄⋅nH₂O (n=1, L=PPh₃, R=Ph ( 2a ) or Tol (=4-MeC₆H₄) ( 2b ); n=0, R=Tol, L=P(pmp)₃ ( 2c ; pmp=4-MeOC₆H₄ or AsPh₃ ( 2d )) are the products of reactions between phosphonium salts (R₃PCH₂CN)ClO₄ (R=Ph or Tol) and [Au(acac)L] (molar ratio 1 : 3, L=PPh₃ or P(pmp)₃; acacH=acetylacetone). The reaction of [Au(acac)PPh₃] with (Ph₃PCH₂CH₂CN)ClO₄ (Au/P 2 – 5) gives the mononuclear complex [Au{CH(PPh₃)CH₂CN}(PPh₃)]ClO₄⋅0.5 H₂O ( 3 ). Complexes 2b or 2c react with [Au(acetone)L]ClO₄ (molar ratio 1 : 1, L=PPh₃ or P(pmp)₃), prepared in situ from [AuCl(L)] and AgClO₄ in acetone, to give the corresponding trinuclear derivatives [(AuL)₂{μ₃-{C(PTol₃)CN}(AuL)}](ClO₄)₂ (L=PPh₃ ( 4a ) or P(pmp)₃ ( 4b )]. We attempted unsuccessfully to prepare single crystals of 4a or 4b or of the triflate salt [{Au(PPh₃)}₂{μ₃-{C(PTol₃)CN}(AuPPh₃)}](TfO)₂⋅H₂O ( 4a′ ), obtained by reacting 4a with 2 equiv. of KCF₃SO₃. In complexes 2 and 4 , two new types of coordination of the ylides R₃P=CHCN are present. Attempts to coordinate three AuL groups to the N-atom of (R₃PCCN)⁻ induced by aurophilicity (see A and B ) were unsuccessful. The reaction between PdCl₂ and R₃P=CHCN (molar ratio 1 : 2) gives trans-[PdCl₂{CH(PTol₃)CN}₂] ( 5 ).     

Dreizentren-oxidative Addition von Phosphor-Yliden an Ru3(CO)12

Three-Centre Oxidative Addition of Phosphorus Ylides to Ru₃(CO)₁₂ Phosphorus ylides undergo oxidative addition to Ru₃(CO)₁₂ to yield a wide range of Ru₃ clusters with triply bridging organic ligands derived from the ylides. Ph₃PCH₂ forms HRu₃(CO)₉(μ₃1-Ph₃P — CH — CO) ( 1 ) containing a phosphonio enolate. Ph₃PCH — CHO yields a product mixture containing the phosphonio enolate-bridged cluster and its PPh₃ derivative 6 , the phosphoniomethylidyne-bridged compound H₂Ru₃(CO)₉(μ₃1-C — PPh₃) ( 5 ), and the ketenylidene-bridged compound H₂Ru₃(CO)₈(PPh₃)(μ₃1-C — CO) ( 7 ). Thermal treatment converts the phosphonio enolate ligand (in 1 ) into the phosphoniomethylidyne ligand (in 5 ), and the latter into the ketenylidene ligand (in 7 ). With Ph₃PCH — C(O)Me and Ru₃(CO)₁₂ ortho1-metalated Ru₃ derivatives 10, 11 of the phosphonio ketone R₃P — C — C(O)Me are produced, and likewise with Ph₃PCH — COOEt the ortho1-metalated derivative 12 of the phosphonio ester R₃P — C — CO₂Et. Me₃PCH — COOtBu is oxidatively added to form HRu₃(CO)₉(μ₃1-Me₃P — C — COOtBu) ( 13 ) bearing a phosphonio ester ligand. — The crystal structures of 6 and 13 are reported. The sequence of Ru₃ clusters and the bonding modes of the μ₃ ligands can be related to the surface reactions during Fischer-Tropsch catalysis.     

Synthese und Struktur von [(Ph3PAu)3NPPh3][PF6]2, einem Gold(I)‐phosphoraniminato‐Komplex

Synthesis and Crystal Structure of [(Ph₃PAu)₃NPPh₃][PF₆]₂, a Gold(I) Phosphoraneiminato Complex The photolytic reaction of Ph₃PAuN₃ with Cr(CO)₆ in THF yields the phosphoraneiminato complex [(Ph₃PAu)₃NPPh₃]²⁺ in low yield as well as the cluster cation [(Ph₃PAu)₈]²⁺ as the main product. The phosphoraneiminato complex crystallizes from CH₂Cl₂ with [PF₆]^? ions as [(Ph₃PAu)₃NPPh₃][PF₆]₂·CH₂Cl₂ in the triclinic space group with a = 1200.8(1), b = 1495.6(2), 2053.5(5), α = 86.97(2)°, β = 82.79(1)°, γ = 81.87(2)°, and Z = 2. The phosphoraneiminato ligand bridges through its N atom three Au atoms, which itself are connected to each other by weak aurophilic interactions.