Carbonyl cationic rhodium(I) and iridium(I) complexes with sulphur donor and triphenylphosphine ligands

Summary The reaction of previously reported Rh^I and Ir^I cationic complexes towards carbon monoxide and triphenylphosphine has been studied. Carbonyl rhodium(I) mixed complexes of the formulae [Rh(CO)L₂(PPh₃)]ClO₄, (L=tetrahydrothiophene(tht), trimethylene sulfide(tms), SMe₂, or SEt₂), [(CO)(PPh₃)Rh{-(L-L)}₂Rh(PPh₃)(CO)](ClO₄)₂ (L-L= 2,2,7,7-tetramethyl-3,6-dithiaoctane (tmdto), (MeS)₂(CH₂)₃ (dth), or 1,4-dithiacyclohexane (dt), [Rh(CO)L(PPh₃)₂]ClO₄ (L= tht, tms, SMe₂, or SEt₂), and carbonyl iridium(I) complexes of the formulae [Ir(CO)₂(COD)(PPh₃)]ClO₄, [Ir(CO)(COD)(PPh₃)₂]ClO₄, [(CO)(COD)(PPh₃) Ir{-(L-L)} Ir(PPh₃)(COD)(CO)](ClO₄)₂ (L-L = tmdto or dt), [(CO)₂ (PPh₃)Ir(-tmdto)Ir(PPh₃)(CO)₂](ClO₄)₂, [(CO)₂(PPh₃) Ir(-dt)₂Ir(PPh₃)(CO)₂](ClO₄)₂, were prepared by different synthetic methods.     

A Dumbbell Shaped Fullerene Dimer with An Inorganic Linker. Addition of C60 and Tetracyanoethylene to Ir2(CO)2Cl2(Ph2P(CH2)nPPh2)2 (n=5 or 7)

The centrosymmetric dimers, ( ²-C₆₀)₂Ir₂(CO)₂Cl₂(-Ph₂P(CH₂)₇PPh₂)₂ and ( ²-TCNE)₂Ir₂(CO)₂Cl₂(-Ph₂P(CH₂)₅PPh₂)₂, have been prepared by the reactions of C₆₀ with Ir₂(CO)₂Cl₂(-Ph₂P(CH₂)₇PPh₂)₂ and of tetracyanoethylene (TCNE) with Ir₂(CO)₂Cl₂(-Ph₂P(CH₂)₅PPh₂)₂, respectively. The structures of both adducts have been elucidated by single crystal X-ray diffraction studies.     

Synthesis and characterization of mononuclear palladium(II) and platinum(II), dinuclear palladium(I) and platinum(I), and heterobimetallic (Pt-Hg or Pt-Ag) complexes containing 1,1-bis-(diphenylphosphino)ethane as ligand

Summary The complex [Pd(dpmMe)₂]Cl₂ [dpmMe = 1,1-bis-(diphenylphosphino) ethane] was prepared from [PdCl₂-(PhCN)₂], whilst [Pd₂X₂(-dpmMe)₂] complexes were prepared from [PdCl₂PhCN₂] and [Pd(PPh₃)₄] (X = Cl), [PdBr( ³-C₃H₅)]₂ (X = Br), or [Pd₂Cl₂(-dpmMe)₂] (X = I). Reaction of [Pd₂Cl₂(-dpmMe)₂] with MeO₂C-C523-01CCO₂Me(L) gave the A-frame complex [PdCl₂(-L) (-dpmMe)₂]. The complexes [PtCl₂(dpmMe)] and [Pt(dpmMe)₂]Cl₂ were prepared from [PtCl₂(Bu ^t CN)₂]. Treatment of either [PtCl₂(dpmMe)] with PhC523-02CLi or [Pt(dpmMe)₂]Cl₂ with MeONa gave [Pt(Ph₂PCMe· PPh₂)₂]. Reaction of [PtCl₂(Bu ^t CN)₂] with [Pt(PPh₃)₄] and dpmMe gave a mixture of [Pt₂Cl₂(-dpmMe)₂] and [PtCl₂(dpmMe)]. The heterobimetallic complexes [Pt(C523-03CPh)₂ (-dpmMe)₂MX] (MX = HgCl₂ or AgCl) were made from the reaction of [Pt(dpmMe)₂]Cl₂ with Hg(C523-04CPh)₂ or Ag(C523-05CPh), respectively. Reaction of the Pt-Hg complex with Na₂S gave [Pt(C523-06CPh)₂ ( ¹-dpmMe)₂]. Oxidative addition of MeI to [PtMe₂· (dpmMe)] gave two Pt^IV isomers of the formula [PtMe₃I(dpmMe)].     

The Addition of Platinum and Palladium Groups to the Disulfido Ligand in Cyclopentadienyl Molybdenum-Manganese Carbonyl Complexes

The reaction of the complexes CpMoMn(CO)₅(-S₂), 2a, Cp=C₅H₅ and Cp*MoMn(CO)₅(-S₂), 2b, Cp*=C₅Me₅with (PPh₃)₂Pt(PhC₂Ph) yielded the new bis-sulfido mixed metal complexes CpMoMn(CO)₅Pt(PPh₃)₂( ₃-S)₂, 3a and Cp*MoMn(CO)₅Pt(PPh₃)₂( ₃-S)₂, 3b by insertion of a platinum metal grouping into the S–S bond. A mono-phosphine complex, Cp*MoMn(CO)₆Pt(PPh₃)( ₃-S)₂, 4b was also isolated from the reaction of 2b with (PPh₃)₂Pt(PhC₂Ph). Compounds 3b and 4b were both characterized crystallographically. Both complexes consist of open MoMnPt clusters with a Mo–Mn single bond, Mo–Mn=2.7570(16) Å for 3b and Mo–Mn=2.7837(13) Å for 4b, and two triply bridging sulfido ligands. The trimetallic complexes CpMo(O)MnPd(PBu ^t ₃)(CO)₅( ₃-S), 5a and Cp*Mo(O)MnPd(PBu ^t ₃)(CO)₅( ₃-S), 5b containing an oxo ligand bonded to molybdenum were obtained from the reaction of 2a–b with Pd(PBu ^t ₃)₂. The molecular structure of the 5a was also established crystallographically.     

Synthesis,spectroscopic investigation and X-ray structure of mononuclear and binuclear oxo complexes of rhenium(V) with pyrazolato ligands

The [{Re(O)Cl(PPh₃)}₂(-O)(-N₂C₃H₃)₂] (1), [{Re(O)Br(PPh₃)}₂(-O)(-N₂C₃H₃)₂] (2), [ReOCl₂{ ²-N₂C₃H₃CMe₂O}(PPh₃)] (3) and [ReOBr₂{ ²-N₂C₃H₃CMe₂O}(PPh₃)] (4) complexes have been synthesized by reacting [ReOX₃(PPh₃)₂] with an excess of pyrazole under different conditions. The rhenium(V) centers of (1) and (2) are linked through two bridging pyrazolato anions and an oxo group. The rhenium(V) atoms in mononuclear complexes (3) and (4) are six coordinated in an octahedral environment with a trans arrangement of the oxo group and oxygen atom of anionic bidentate ligand C₃H₃N₂C(Me)₂O^– formed in the reaction of pyrazole and Me₂CO.     

Synthesis and crystal structure of a cubane-like molybdenum copper sulphur bromide cluster [MoCu3S3Br(SCH2CH2S)(PPh3)3]·MeCN

Summary [MoCu₃S₃Br(SCH₂CH₂S)(PPh₃)₃]·MeCN, MW=1382.78, space group Pl, has the triclinic cell parametersa=12.272(11),b=13.172(7),c=20.363(3)Å, =106.26(3)^o, =95.64(5)^o, =65.79(6)^o; Z=2, V=2881.4ų. Dc=1.55 g cm^–3. MoK radiation. =0.71073Å, =22.8 cm^–1. F(000)=1348. R=0.69 for 4964 observed unique reflections [I>3(I)]. There are some distortions in the cubane-like MoCu₃S₃Br core, with three form Mo–Cu bonds. The Mo atom is bound by chelating SCH₂CH₂S and three ₃-S atoms.     

Reactions of trans-[OsO2Cl2L2] (L = PPh3, AsPh3, SbPh3) with Acetic Acid

The possibility of reactions between trans-[OsO₂Cl₂L₂] (L = PPh₃, AsPh₃, SbPh₃) osmium(VI) complexes and glacial acetic acid to give osmium(IV) compounds of general formula [Os₂(-O)(-O₂CCH₃)₂Cl₄(L)₂] was studied.     

Synthesis and characterization of some rhodium(III) cyclometallated complexes of 2-substituted benzylideneamino thiazoles

Summary Schiffs bases derived from 2-aminothiazole and substituted benzaldehydes were reacted with [RhCl(PPh₃)₃] or [Rh(-Cl)(COD)]₂ (COD = 1,5-cyclooctadiene) in the presence of four equivalents of PPh₃ to give Rh^III cyclometallated complexes of the type [RhHCl{(X-benzylidene) thiazole}(PPh₃)₂], in which the imine C-H added oxidatively to the metal. The complexes were characterized using i.r., u.v. and n.m.r. spectroscopy. The disposition of the hydride ligand was inferred as trans to a N-donor ligand.     

The X-ray Structure, Electrochemistry and Catalytic Reactivity of Os4Au(μ-H)3(CO)12(PPh3) Towards the Oxidative Carbonylation of Aniline

The reaction of the anion [Os₄(-H)₃(CO)₁₂]^– with one equivalent of Au(PPh₃)Cl affords [Os₄Au(-H)₃(CO)₁₂(PPh₃)] (1), the structure of which was established by single crystal X-ray analysis. Its electrochemical behavior and catalytic properties are also reported. This bimetallic cluster catalyses the oxidative carbonylation of aniline to give methyl phenylcarbamate in methanol with good conversion and selectivity compared to the homometallic [Os₄(-H)₄(CO)₁₂] cluster.     

Preparation and x-ray structure analysis of [Rh2Cl2(μ-CO)(μ-vdpp)2] [vdpp=H2C=C(PPh2)2]

Summary The complex [Rh₂Cl₂(-CO)(-vdpp)₂] (1) (vdpp=H₂C=C(PPh₂)₂) was prepared by reaction of [Rh₂(CO)₄-(-Cl)₂] with vdpp. When (1) is allowed to stand overnight under an atmosphere of CO without stirringtrans-[Rh₂Cl₂(CO)₂(-vdpp)₂] is formed as a red precipitate in low yields. On rapid addition of CO the tricarbonyl complex [Rh₂(CO)₂(-CO)(-Cl)(-vdpp)₂]-Cl is formed instead. The chemical behaviour of the vdpp-substituted complex (1) is very similar to that of the corresponding dppm-substituted complex [Rh₂(Cl₂-(-CO)(-dppm)₂] (dppm=H₂C(PPh₂)₂). this similarity also extends to the molecular structures of both compounds. Unit cell parameters of (1): space group Pben (Z=8),a=2344.7(5),b=1506.9(7),c=3021.6(9)pm. Rh-Rh 267.4(1) pm.     

Platinum(II) pyridine-2-thiolate and -selenolate complexes

The reaction of [Pt₂X₂(-Cl)₂(PR₃)₂] with NaSpy or NaSepy gave complexes of the type [PtX(Epy)(PR₃)]_n (X=Cl or Ar; E=S or Se; PR₃=PEt₃, PMe₂Ph, PMePh₂ or PPh₃; n=1 or 2) which were characterized by elemental analysis and by ¹H, ³¹P{¹H}, ¹⁹⁵Pt{¹H} n.m.r. spectroscopy. When X=Cl a dynamic equilibrium between [Pt₂Cl₂(-Spy)₂(PR₃)₂] and [PtCl(k-S,N-Spy)(PR₃)] species exists in CHCl₃ solution. The aryl derivatives, X=Ar, exist exclusively as dimers (n=2) with predominantly SN bridging. The [Pt(Spy)₂ (PPh₃)₂] complex, prepared by reacting [PtCl₂ (PPh₃)₂] with NaSpy, dissociates in CHCl₃ to [Pt(k-S,N-Spy) (Spy)(PPh₃)] and PPh₃ at room temperature.     

Trinuclear Gold(I) Complexes with Various Coordination Modes of N,N-dimethyldithiocarbamate

The compounds [Au₃(S₂CNMe₂)₃{ ₃-(PPh₂)₃CH]} (1) and [Au₃(S₂CNMe₂)(-S₂CNMe₂){ ₃-(PPh₂)₃CH}]ClO₄ (2) are obtained by reaction of [Au₃Cl₃{ ₃-(PPh₂)₃CH}] with three equivalents of sodium dimethyldithiocarbamate or two equivalents of the same reagent in the presence of excess NaClO₄. Reaction of 2 with the group 11 metal complexes [AuCl(tht)], CuCl or [Au(C₆F₅)(tht)] takes place with displacement of [M(S₂CNMe₂)]_n (M=Cu, Au) and formation of the new complexes [Au₃X(-S₂CNMe₂){ ₃-(PPh₂)₃CH}]ClO₄ (X=Cl (3), X=C₆F₅ (4)); further reaction of 3 with [Ag(OClO₃)(tht)] (tht=tetrahydrothiophene) affords the dicationic species [Au₃(-S₂CNMe₂){ ₃-(PPh₂)₃CH}(tht)](ClO₄)₂ (5). Treatment of [Au₃Cl₃{ ₃-(PPh₂)₃CH}] with one equivalent of NaS₂CNMe₂ allows the substitution of only one chlorine atom, giving rise to the complex [Au₃Cl₂(S₂CNMe₂){ ₃-(PPh₂)₃CH}] (6), in which the dithiocarbamate ligand acts as monodentate rather than bidentate bridging as observed in compounds 3–5. The crystal structures of complexes 1 and 2 have been established by X-ray diffraction studies and show close gold–gold contacts.     

Mono and dinuclear cationic rhodium(I) and iridium(I) complexes with sulphur donor and group Vb ligands

Summary Rhodium(I) and iridium(I) mixed complexes of the formulae [M(diolefin)LL]ClO₄, [M(diolefin)L₂L]ClO₄, [(diolefin)LIr(-L)₂IrL(diolefin)](ClO₄)₂, [(diolefin)LM(-L-L)ML'(diolefin)](ClO₄)₂, [(diolefin)Rh{-(L-L)}₂Rh(PPh₃)₂](ClO₄)₂ and [(diolefin)LIr{-(L-L)}₂IrL (diolefin)](C1O₄)₂, (L=monodentate sulphur ligand, L-L=bidentate sulphur ligand, L=group Vb ligand; M=Rh, diolefin=1,5-cyclooctadiene (COD) or 2,5-norbornadiene (NBD); M=Ir, diolefin=COD) are described.Author to whom all correspondence should be directed.     

Cluster chemistry. 85. Addition of a gold acetylide to an Ru5 cluster. X-ray structure of AuRu5(μ5-C2PPh2)(μ-C2Ph)(μ-PPh2)(CO)13(PPh3)

The reaction between Ru₅(₅-C₂PPh₂)(-PPh₂)(CO)₁₃ and Au(C₂Ph)(PPh₃) afforded AuRu₅(₅-C₂PPh₂)(-C₂Ph)(-PPh₂)(CO)₁₃ (PPh₃), in which the Ru₅ cluster has a scorpion geometry; the Au(PPh₃) group bridges one of the Ru-Ru bonds of the Ru₃ triangle, while the C₂Ph group bridges one of the tail Ru-Ru vectors.For Part 84, see Ref. 1.     

Reactions of ReH3(CO)(PMe2Ph)3 with Metallic Lewis Acids. Synthesis and Structural Characterization of Hydrido-Bridged Heterometallic Rhenium-Gold, Rhenium-Silver, and Rhenium-Copper Complexes

This contribution presents a study of the reactions of ReH₃(CO)(PMe₂Ph)₃ (1) with a variety of metallic Lewis acids of the coinage metals to form hydrido-bridged heterometallic rhenium-gold, rhenium-silver, and rhenium-copper complexes. The reaction of 1 with AuCl(PPh₃) proceeds with elimination of hydrogen to give the hydrido-bridged heterobinuclear rhenium-gold complex (PMe₂Ph)₃(CO)ClRe(-H)Au(PPh₃) (2). In contrast, the reactions of 1 with AgPF₆, [Cu(CH₃CN)₄]PF₆ or CuCl proceed without elimination of hydrogen to give the hydrido-bridged heterotrinuclear rhenium-silver and rhenium-copper complexes [(PMe₂Ph)₃(CO)HRe(-H)₂M(-H)₂ReH(CO)(PMe₂Ph)₃]PF₆ (M=Ag (3), Cu (4)) and the hydrido-bridged heterotetranuclear rhenium-copper complex (PMe₂Ph)₃(CO)HRe(-H)₂Cu(-Cl)₂Cu(-H)₂ReH(CO)(PMe₂Ph)₃ (5), respectively. The molecular structures of compounds 2 and 3 have been determined by single-crystal X-ray diffraction studies. Crystallographic data for 2: monoclinic, space group P2₁2₁2₁, a=12.804(2) Å, b=13.512(2) Å, c=24.312(3) Å, V=4206(1) ų, Z=4, and R=0.042. Crystallographic data for 3: monoclinic, space group C2/c, a=24.212(6) Å, b=13.098(3) Å, c=20.177(5) Å, b=116.40(2)°, V=5732(2) ų, Z=4, and R=0.044. The X-ray crystal structure of 2 exhibits a short contact (2.798(12) Å) between the gold atom and the CO ligand that is primarily bound to the adjacent rhenium atom, suggesting an incipient semibridging relationship.     

Bimetallic group 6 metal tetracarbonyls doubly bridged by bisphosphine and/or dithiaalkane ligands

A series of [W(CO)₄]₂(-dppa)(-DTA) type complexes [dppa = Ph₂P(CH₂) _n PPh₂, n = 2(dppe), 4(dppb), 6(dpph), 10(dppd); DTA = ^t BuS(CH₂) _m S ^t Bu, m = 3(DTN), 4(DTD), 5(DTUD), 6(DTDD)] containing doubly bridged bisphosphine and dithiaalkane ligands have been prepared by stepwise replacement of piperidine (pip) from cis-W(CO)₄(pip)₂ complex. In addition, complexes of general formulae [W(CO)₄]₂(-dppa)₂ and [Mo(CO)₄]₂(-DTA)₂ have been prepared by similar methods. These new complexes have been characterized by i.r. spectroscopy and elemental analysis.     

Mikrogravimetrische Bestimmung von Gold als Dekamethonium-Tetrabromoaurat(III)

Zusammenfassung Die mikrogravimetrische Bestimmung von Gold als Bis(trimethyl)-dekamethylendiammoniumtetrabromoaurat(III) [(CH₃)₃N-(CH₂)₁₀-N(CH₃)₃] [AuBr₄]₂ erlaubt die Erfassung von 700g Au neben 200fachen Überschüssen an Cu²⁺ und Ni²⁺ sowie 50fachen Mengen anderer Übergangsmetalle.

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Summary The microgravimetric determination of gold as bis-(trimethyl) decamethylenediammoniumtetrabromaurate(III) [(CH₃)₃N-(CH₂)₁₀-N(CH₃)₃] [AuBr₄]₂ permits the determination of 700g Au in the presence of 200-fold excesses of Cu²⁺ and Ni²⁺ as well as 50-fold amounts of other transition metals.

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Résumé Le microdosage gravimétrique de l'or à l'état de tétrabromoaurate-III de bis(triméthyl)décaméthylènediammonium [(CH₃)₃N-(CH₂)₁₀-N(CH₃)₃] [AuBr₄]₂ permet de descendre jusqu'à 700g Au en présence d'un excès de 200 fois Cu²⁺ et Ni²⁺ et d'une quantité 50 fois plus grande des autres métaux de transition.

     

Reactions of the dinitrogen complextrans-[ReCl(N2)(dppe)2] with thiolate compounds and with carbon bisulphide

Summary The complextrans-[ReCl(N₂)(dppe)₂], (1) reacts with the thiolate salts Li[SC₆H₄Me-4], Tl[SC₆H₄Me-4] and [Pb(SBu-t)₂] to yield [ReCl(SC₆H₄Me-4)(dppe)₂], [Re(SC₆H₄Me-4) (dppe)₂] and [{ReO(dppe)}₂(-Cl)(-S)(-SBu-t)] (tentative formulation), respectively. The [ReCl(²-CS₂)(dppe)₂] complex appears to be formed by reaction of (1) with CS₂.     

Synthesis of Palladium Clusters with the P--N--P Assembling Ligands (Ph2P)2CH2 (dppm) and (Ph2P)2NH (dppa). Crystal Structure of [Pd4(μ-Cl)2(μ-dppm)2(μ-dppa)2](PF6)2

Tetrapalladium clusters containing dppa or dppa and dppm bridging ligands were prepared by condensation of dinuclear units. Reaction of [Pd₂Cl₂(-dppa)₂] with [Cu(PPh₃)]PF₆ (generated in situ in THF) yielded [Pd₄(-Cl)₂(-dppa)₄] (PF₆)₂ (4) in a virtually quantitative yield but [Pd₄(-Cl)₂(-dppm)₂(-dppa)₂] (PF₆)₂ (6) was best prepared in CH₂Cl₂ from [Pd₂Cl₂(-dppm)₂] and [Pd₂(MeCN)₂(-dppa)₂](PF₆)₂ (2). The structure of 6·2(CH₃)₂CO·2H₂O was determined by X-ray diffraction. It consists of a planar, centrosymmetric 10-membered ring structure. The four bridging diphosphine ligands are of two types: two dppa ligands support the Pd Pd bonds [2.6055(4) Å], whereas the two dppm ligands bridge between two palladium atoms separated by 3.722(4) Å, which are also bridged by a chloride ligand.     

Reaction of group 13 sulfido cubanes with dimethylzirconocene

The reaction of Cp₂ZrMe₂ with the aluminum- and gallium-sulfido cubane compounds [( ¹ Bu)M(₃-S)]₄ (M = Al, Ga), has been followed by NMR spectroscopy. Cleavage of the M₄S₄ core occurs resulting in abstraction of a monomeric ( ¹ Bu)M(S) moiety and yielding Cp₂Zr(-S)(-Me)Al( ¹ Bu)Me (1) and [Cp₂Zr(/gm-S)]₂,[Ga( ¹ Bu)Me₂]₂ (3), respectively. The remaining ( ¹ Bu)₃M₃S₃ fragment reacts further with Cp₂ZrMe₂ to give [(Cp₂Zr)M₃(₃-S)₃ ( ¹ Bu)₃Me₂], M = Al (2), Ga (4). The molecular structure of [(Cp₂Zr)Ga₃,(₃-S)₃('Bu)₃Me₂] (4) has been confirmed by X-ray crystallography. All these compounds subsequently decompose to [Cp₂Zr(-S)]₂ and M( ¹ Bu)Me₂. The structure of compound 3 is discussed with respect to the decreased propensity of gallium, as compared to aluminum, to form 3-center 2-electron bridging bonds. Crystal data for [(Cp₂Zr)Ga₃(₃-S)₃( ¹ Bu)₃Me₂] (4): monoclinic, P2₁/n,a = 10.585(2),b = 17.970(4),c = 16.418(3) A, = 101.00(3)°, R = 0.0402, R _w = 0.0402.