Nickel(O)-Komplexe mit anionischen Liganden des Typs E(C6H5) (E = Si,Ge, Sn)

Nickel(O) Complexes with the Anionic Ligands E (C₆H₅)^?₃ (E = Si, Ge, Sn) Complexes of the type Me^I_XNi(EPH₃)_X(THF)_Y are formed from Ni(COD)₂ by substitution with Me^IEPh₃ (E = Si, Ge, Sn) in THF (COD = Cyclooctadiene-1,5). In the case of the ligands GePh^?₃ and SnPh^?₃ nickel(O) is fourfold coordinated, but in the case of SiPh^?₃ it is only two-fold or threefold coordinated. Products of the reaction between Ni(COD)₂ and LiPbPh₃ are Li₂Ni(COD)Ph₂(THF)₅ and Ph₃PbPbPh₃. The ¹H-n.m.r., ²⁹Si-n.m.r., and ¹¹⁹Sn-Mössbauer spectra of the complexes Me^I_XNi(EPh₃)_X(THF)_Y are compared with the spectra of the corresponding alkali compounds Me^IEPh₃. The magnetic anisotropy effects of the atomes Ge, Sn, Pb and Ni are of high importance for ¹H- and ²⁹Si-chemical shifts. The donor action of SnPh^?₃ is shown by the Mössbauer spectrum of Na₄Ni(SnPh₃)₄(THF)₄. But there is no direct evidence of π-back donation in the compound.     

Darstellung und Strukturen neuartiger Triphenylsilylund Triphenylgermyl‐substituierter Gallane und Oligogallane – [Ga3(GePh3)6]–, das erste lineare Trigallan

Chemistry of Gallium. 20. Synthesis and Structures of Novel Triphenylsilyl and Triphenylgermyl Substituted Gallanes and Oligogallanes – [Ga₃(GePh₃)₆]^–, the First Linear Trigallane From the raction of sonochemically prepared “GaI” with LiEPh₃ (E = Si, Ge) the compounds [Li(THF)₂][GaI(EPh₃)₃] (E = Si: 22 , E = Ge: 24 ), [Li(THF)₄][GaI(SiPh₃)₃] ( 23 ), [Li(THF)₄][Ga₂(SiPh₃)₅] ( 21 ) and [Li(THF)₄][Ga₃(GePh₃)₆] ( 25 ) as well as polymeric Li(THF)I ( 20 ) were obtained and structurally characterized. 21 is a monoanionic digallane, exhibiting a trigonal planar and a tetrahedrally coordinated gallium centre. 25 has a linear Ga₃ core, where the terminal gallium atoms bear three GePh₃‐groups, each. The central Ga atom is only 2‐coordinated. Thus, 25 may be a valuable hint to the formation of larger gallium clusters with “naked” gallium atoms. Derivatives of 21 and 25 have been studied by DFT methods.     

Formation of the Salt‐like Complexes [Co{S2CC(PPh3)2}3][Co(CO)4]3 and [(CO)4Mn{S2CC(PPh3)2}][Mn(CO)5] from the Reaction of the Related Carbonyl Compounds with S2CC(PPh3)2

The betain‐like compound S₂CC(PPh₃)₂ ( 1 ), which is obtained from CS₂ and the double ylide C(PPh₃)₂, reacts with [Co₂(CO)₈] and [Mn₂(CO)₁₀] in THF to afford the salt‐like complexes [Co{S₂CC(PPh₃)₂}₃][Co(CO)₄]₃ ( 2 ) and [(CO)₄Mn{S₂CC(PPh₃)₂}][Mn(CO)₅] ( 3 ), respectively, in good yields. At both d⁶ cations 1 acts as a chelating ligand. Disproportionation reactions from formal Co⁰ into Co^III and Co^?I and from Mn⁰ into Mn^I and Mn^?I occurred with the removal of four or one carbonyl groups, respectively. The crystal structures of 2· 5.5THF and 3· 2THF are reported, which show a shortening of the C–C bond in the ligand upon complex formation. The compounds are further characterized by ³¹P NMR and IR spectroscopy.     

Rhodium Complexes Containing O‐Bonded NHxMe2−xCHO (x=0, 1, 2): X‐Ray Structure of [Rh(PPh3)3(OCHNHMe)]ClO4

Displacement of norbornadiene (nbd; bicyclo[2.2.1]hepta‐2,5‐diene) from [Rh(PPh₃)₂(nbd)]ClO₄ by hydrogenation in the presence of PPh₃ and formamide or Me‐substituted derivatives, results in the formation of O‐bonded formamide complexes [Rh(PPh₃)₃(OCHNH_xMe_2−x)]ClO₄ (x=0, 1, 2) rather than N‐bonded derivatives. These have been characterised by spectroscopic measurements and, in the case of [Rh(PPh₃)₃(OCHNHMe)]ClO₄, by X‐ray crystallography. All undergo oxidative addition with H₂, and the rates of ligand exchange in the Rh^I and Rh^III complexes have been determined by magnetisation‐transfer measurements.     

Einfache Trithio- und Perthiocarbonatokomplexe mit interessanter Koordinationschemie: [E(CS3)2]2− (E = Sn,Zn, Cd), [E(CS3)3]3− (E = As,Sb, Bi,Co), {Cu(CS3)−}∞ und [Zn(CS4)2]2−

Simple Trithio- and Perthiocarbonato Complexes with Interesting Bond Properties: [E(CS₃)₂]^2? (E = Sn, Zn, Cd), [E(CS₃)₃]^3? (E = As, Sb, Bi, Co), {Cu(CS₃)^?}_∞ and [Zn(CS₄)₂]^2? By reactions of potassium trithiocarbonate ( 1 ) with solutions of zinc(II)- acetylacetonate, cadmium(II)-chloride, tin(II)-chloride, arsenic(III)-sulfide (suspension), antimony(III)-chloride, bismuth(III)-chloride and copper(II)-chloride in dimethyl sulfoxide, as well as of trisodium hexanitrito cobaltate(III) in water, and the precipitation of the complexes with an aqueous solution of tetraphenylphosphonium chloride the compounds (PPh₄)₂[Zn(CS₃)₂] ( 2 ), (PPh₄)₂[Cd(CS₃)₂] ( 3 ), (PPh₄)₂[Sn(CS₃)₂] ( 4 ), (PPh₄)₃[As(CS₃)₃] ( 5 ), (PPh₄)₃[Sb(CS₃)₃] ( 6 ), (PPh₄)₃[Bi(CS₃)₃] ( 7 ), (PPh₄)₃[Co(CS₃)₃] ( 8 ) and (PPh₄)Cu(CS₃) ( 9 ) have been isolated. (PPh₄)₂[Zn(CS₄)₂] · CH₃NO₂ ( 10 ) has been prepared by heating a solution of 2 in nitromethane to 60--70°C in presence of air. The reaction of 1 in dimethyl sulfoxide with an aqueous tetraphenylphosphonium chloride solution in presence of oxygen leads to (PPh₄)₂[C₂S₆] ( 11 ). The compounds have been characterized by spectroscopical studies (IR, Raman, UV/Vis, ¹¹³Cd/⁵⁹Co-NMR), magnetic susceptibility measurements, powder diffractometry, elemental analyses and single crystal X-ray structure analysis ( 4 – 7 , 10 and 11 ). The difficult growing of single crystals has been reported in detail. For crystal data see Inhaltsübersicht.     

Ruthenium(II) and ruthenium(III) complexes derived from O,O-donor ligands

The new [Ru¹¹(PPh₃)₂L₂] complexes [L=monoanion of tropolone, benzoylacetone, or 3-hydroxy-2-pyridinone (hypy)], [RuH(PPh₃)₃L′][HL′=maltol, dibenzoylmethane or 1,2-dimethyl-3-hydroxy-4-pyridinone (Hdmhypy)] and [Ru^IIIX₂(EPh₃)₂L″] complexes (X=Cl, Br; E=As or P; L″=hypy, dmhypy) have been prepared, and characterized by spectroscopic techniques. Their redox behaviour was studied by cyclic voltammetry. Most of the complexes were found to be effective catalysts for the oxidation ofp-methoxybenzyl alcohol to the corresponding aldehyde in the presence ofN-methylmorpholine-N-oxide as co-oxidant.     

Gold(I) and Gold(III) Trifluoromethyl Derivatives

Trifluoromethylation of AuCl₃ by using the Me₃SiCF₃/CsF system in THF and in the presence of [PPh₄]Br proceeds with partial reduction, yielding a mixture of [PPh₄][Au^I(CF₃)₂] ( 1′ ) and [PPh₄][Au^III(CF₃)₄] ( 2′ ) that can be adequately separated. An efficient method for the high‐yield synthesis of 1′ is also described. The molecular geometries of the homoleptic anions [Au^I(CF₃)₂]^? and [Au^III(CF₃)₄]^? in their salts 1′ and [NBu₄][Au^III(CF₃)₄] ( 2 ) have been established by X‐ray diffraction methods. Compound 1′ oxidatively adds halogens, X₂, furnishing [PPh₄][Au^III(CF₃)₂X₂] (X=Cl ( 3 ), Br ( 4 ), I ( 5 )), which are assigned a trans stereochemistry. Attempts to activate C? F bonds in the gold(III) derivative 2′ by reaction with Lewis acids under different conditions either failed or only gave complex mixtures. On the other hand, treatment of the gold(I) derivative 1′ with BF₃?OEt₂ under mild conditions cleanly afforded the carbonyl derivative [Au^I(CF₃)(CO)] ( 6 ), which can be isolated as an extremely moisture‐sensitive light yellow crystalline solid. In the solid state, each linear F₃C‐Au‐CO molecule weakly interacts with three symmetry‐related neighbors yielding an extended 3D network of aurophilic interactions (Au???Au=345.9(1) pm). The high $\tilde \nu $ _CO value (2194 cm^?1 in the solid state and 2180 cm^?1 in CH₂Cl₂ solution) denotes that CO is acting as a mainly σ‐donor ligand and confirms the role of the CF₃ group as an electron‐withdrawing ligand in organometallic chemistry. Compound 6 can be considered as a convenient synthon of the “Au^I(CF₃)” fragment, as it reacts with a number of neutral ligands L, giving rise to the corresponding [Au^I(CF₃)(L)] compounds (L=CNtBu ( 7 ), NCMe ( 8 ), py ( 9 ), tht ( 10 )).     

New heteroorganic betaines containing the (+)E15—C—E14—X(–) and (+)E15—C—E14(–) structural fragments (E15 = P,As; E14 = Si,Ge, Sn; X = C,S, O,NR)

The review surveys the data on the reactions of phosphorus and arsenic ylides with compounds containing E=X bonds (E = C, Si, Ge, or Sn; X = C or S), cyclic oligomers (R₂ES)_n (n = 2 or 3), and heavier analogs of carbenes. These reactions give rise to two new classes of heteroorganic betaines containing the ⁽⁺⁾E¹⁵—C—E¹⁴—X^(–) (I) and ⁽⁺⁾E¹⁵—C—E^14(–) (II) (E¹⁵ = P or As; E¹⁴ = Si, Ge, or Sn; X = C or S) structural fragments. Procedures for the synthesis of these compounds, their reactivities, the X-ray diffraction structures, and the electronic structures established by high-level quantum-chemical calculations are considered in detail. The carbon analogs of betaines of type I, viz., compounds bearing the ⁽⁺⁾P—C—C—X^(–) fragment (III), are also discussed. The latter were long considered as possible intermediates in the reactions of compounds containing the polar C=X bond (X = C, O, S, NR, etc.) with phosphorus ylides (classical Wittig and Corey—Chaykovsky reactions and related processes).     

Transition‐Metal Complexes of Tetrylones [(CO)5W‐E(PPh3)2] and Tetrylenes [(CO)5W‐NHE] (E=C–Pb): A Theoretical Study

Quantum chemical calculations at the BP86/TZVPP//BP86/SVP level are performed for the tetrylone complexes [W(CO)₅‐E(PPh₃)₂] ( W‐1 E ) and the tetrylene complexes [W(CO)₅‐NHE] ( W‐2 E ) with E=C–Pb. The bonding is analyzed using charge and energy decomposition methods. The carbone ligand C(PPh₃) is bonded head‐on to the metal in W‐1 C , but the tetrylone ligands E(PPh₃)₂ are bonded side‐on in the heavier homologues W‐1 Si to W‐1 Pb . The W? E bond dissociation energies (BDEs) increase from the lighter to the heavier homologues ( W‐1 C : D_e=25.1 kcal mol^?1; W‐1 Pb : D_e=44.6 kcal mol^?1). The W(CO)₅←C(PPh₃)₂ donation in W‐1 C comes from the σ lone‐pair orbital of C(PPh₃)₂, whereas the W(CO)₅←E(PPh₃)₂ donation in the side‐on bonded complexes with E=Si–Pb arises from the π lone‐pair orbital of E(PPh₃)₂ (the HOMO of the free ligand). The π‐HOMO energy level rises continuously for the heavier homologues, and the hybridization has greater p character, making the heavier tetrylones stronger donors than the lighter systems, because tetrylones have two lone‐pair orbitals available for donation. Energy decomposition analysis (EDA) in conjunction with natural orbital for chemical valence (NOCV) suggests that the W? E BDE trend in W‐1 E comes from the increase in W(CO)₅←E(PPh₃)₂ donation and from stronger electrostatic attraction, and that the E(PPh₃)₂ ligands are strong σ‐donors and weak π‐donors. The NHE ligands in the W‐2 E complexes are bonded end‐on for E=C, Si, and Ge, but side‐on for E=Sn and Pb. The W? E BDE trend is opposite to that of the W‐1 E complexes. The NHE ligands are strong σ‐donors and weak π‐acceptors. The observed trend arises because the hybridization of the donor orbital at atom E in W‐2 E has much greater s character than that in W‐1 E , and even increases for heavier atoms, because the tetrylenes have only one lone‐pair orbital available for donation. In addition, the W? E bonds of the heavier systems W‐2 E are strongly polarized toward atom E, so the electrostatic attraction with the tungsten atom is weak. The BDEs calculated for the W? E bonds in W‐1 E , W‐2 E and the less bulky tetrylone complexes [W(CO)₅‐E(PH₃)₂] ( W‐3 E ) show that the effect of bulky ligands may obscure the intrinsic W? E bond strength.     

Vibrational spectrum of nasicon-like,rhombohedral orthophosphates MIMIV2(PO4)3

The Raman and i.r. spectra of nasicon-type M^IM^IV₂(PO₄)₃ rhombohedral phosphates (M^I = Li, Na, K, Rb, Cs, Tl; M^IV = Ge, Sn, Ti, Zr, Hf) exhibit intricate relationships between the spectra and the chemical composition. The pattern of the PO₄ stretching frequencies is more or less strongly modified by the nature of both M^IV and M^I cations. Still greater variations are observed in the medium and low frequency region, although some external modes have been identified by the study of mass effects (⁶Li⁷Li, ⁷⁰Ge⁷⁶Ge, ZrHf etc.). The origin of this complex behaviour is discussed in relation to the structure.     

The reactions of Ir(CO)Cl(PPh3)2 with HSnPh3

A reinvestigation of the reaction of Ir(CO)Cl(PPh₃)₂, 1 with HSnPh₃ has revealed that the oxidative-addition product Ir(CO)Cl(PPh₃)₂(H)(SnPh₃), 2 has the H and SnPh₃ ligands in cis-related coordination sites. Compound 2 reacts with a second equivalent of HSnPh₃ by a Cl for H ligand exchange to yield the new compound H₂Ir(CO)(SnPh₃)(PPh₃)₂, 3. Compound 3 contains two cis- related hydride ligands. Under an atmosphere of CO, 1 reacts with HSnPh₃ to replace the Cl ligand with SnPh₃ and one of the PPh₃ ligands with a CO ligand and also adds a second equivalent of CO to yield the 5-coordinate complex Ir(CO)₃(SnPh₃)(PPh₃), 4. Compound 4 reacts with HSnPh₃ by loss of CO and oxidative addition of the Sn-H bond to yield the 6-coordinate complex HIr(CO)₂(SnPh₃)₂(PPh₃), 5 that contains two trans-positioned SnPh₃ ligands.     

Synthesis,characterization and catalytic studies of ruthenium(II) chalconate complexes

Stable ruthenium(II) carbonyl complexes of the type [RuCl(CO)(EPh₃)(B)(L)] (E = P or As; B = PPh₃, AsPh₃ or Py; L = 2′‐hydroxychalcones) were synthesized from the reaction of [RuHCl(CO)(EPh₃)₂(B)] (E = P or As; B = PPh₃, AsPh₃ or Py) with 2′‐hydroxychalcones in benzene under reflux. The new complexes were characterized by analytical and spectroscopic (IR, electronic ¹H, ³¹P and ¹³C NMR) data. They were assigned an octahedral structure. The complexes exhibited catalytic activity for the oxidation of primary and secondary alcohols into their corresponding aldehydes and ketones in the presence of N‐methylmorpholine‐N‐oxide (NMO) as co‐oxidant and were also found to be efficient transfer hydrogenation catalysts. Copyright © 2008 John Wiley & Sons, Ltd.     

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.     

Darstellung von Germanium-Mangan-, Germanium-Rhenium- und Zinn-Rhenium-Clustern des Typs M2(CO)8[μ-EXM(CO)5]2, (M = Mn,E = Ge,X = Br,I; M = Re,E = Ge bzw. Sn,X = I bzw. Cl,Br, I)

Preparation of Germanium-Manganese-, Germanium-Rhenium- and Tin-Rhenium-Clusters of the Type M₂(CO)₈[μ-EXM(CO)₅]₂ (M = Mn, E = Ge, X = Br, I; M = Re, E = Ge or Sn, X = I or Cl, Br, I) The clusters Re₂(CO)₈[μ-SnXRe(CO)₅]₂ are prepared by reaction of Re₂(CO)₁₀ and SnX₂ in a Schlenk-tube under release of pressure (X = Cl, Br, I) or in a sealed glass tube (X = Br, I). As central structural unit a four-membered Re₂Sn₂ ring has to be assumed. This unit can be opened again by reaction with CO under pressure. X₂Sn[Re(CO)₅]₂, which is also formed during the preparation of the clusters in dependance of the CO-pressure, indicates insertion of SnX₂ into the Re—Re bond to be the primary step. The corresponding clusters M₂(CO)₈[μ-GeXM(CO)₅]₂ (M = Mn, X = Br, I; M = Re, X = I) are prepared by reaction of GeI₂ and M₂(CO)₁₀ or of I₂Ge[Mn(CO)₅]₂ and Mn₂(CO)₁₀ or of Br₃GeMn(CO)₅ and BrMn(CO)₅. Ir frequencies of the new clusters are assigned.     

Synthesis and characterization of new sulfide aggregates of the type [{Pt2(μ3-S)2(P-P)2}M(C6F5)2] (M=Ni, Pd, Pt; P-P=2PPh3, 2PMe2Ph, dppf)

The reaction of [Pt₂(μ-S)₂(P-P)₂] (P-P=2PPh₃, 2PMe₂Ph, dppf) [dppf=1,1^′-bis(diphenylphosphino)ferrocene] with cis-[M(C₆F₅)₂(PhCN)₂] (M=Ni, Pd) or cis-[Pt(C₆F₅)₂(THF)₂] (THF=tetrahydrofuran) afforded sulfide aggregates of the type [{Pt₂(μ₃-S)₂(P-P)₂}M(C₆F₅)₂] (M=Ni, Pd, Pt). X-ray crystal analysis revealed that [{Pt₂(μ₃-S)₂(dppf)₂}Pd(C₆F₅)₂], [{Pt₂(μ₃-S)₂(PPh₃)₂}Ni(C₆F₅)₂], [{Pt₂(μ₃-S)₂(PPh₃)₂}Pd(C₆F₅)₂] and [{Pt₂(μ₃-S)₂(PMe₂Ph)₂}Pt(C₆F₅)₂] have triangular M₃S₂ core structures capped on both sides by μ₃-sulfido ligands. The structural features of these polymetallic complexes are described. Some of them display short metal-metal contacts.     

Oximato bridged RhIII2MII and RhIIIMI species (MII = Mn, Co, Ni; MI = Cu, Ag)

The reaction of [RhCl₂(HPhL)(PhL)] with M^II(ClO₄)₂·6H₂O in presence of alkali has furnished trinuclear [RhCl₂(PhL)₂]₂M(H₂O)₂·H₂O (HPhL is phenylazobenzaldoxime; M = Mn, Co, Ni). A similar reaction with M^I(PPh₃)₂NO₃ yielded binuclear [RhCl₂(PhL)₂]M(PPh₃)₂ (M = Cu, Ag). In these molecules the oximato group acts as a bridge between Rh^III (bonded at N) and M^II or M^I (bonded at O). In structurally characterized [Rh^IIICl₂(PhL)₂]₂Mn(H₂O)₂.H₂O the centrosymmetric distorted octahedral MnO₆ coordination sphere is spanned by four oximato oxygen atoms and two water molecules lying in trans position. In the lattice the neighbouring molecules are held together by H₂O⋯H₂O⋯H₂O hydrogen bonds generating infinite zigzag chains. The manganese atoms lie parallel to the C-axis, the shortest Mn...Mn distance being 7.992 ?. Magnetic exchange interactions if any are small as seen in room temperature magnetic moments. The manganese system displays a strong EPR signal near g = 2.00. In the complex [RhCl₂(PhL)₂]Cu(PPh₃)₂ the copper atom is coordinated to two oximato oxygen atoms and the two phosphorus atoms in a distorted tetrahedral geometry. The softness of the phosphine ligand is believed to sustain the stable coordination of hard oximato oxygen to soft Cu^I. The coordination sphere of the RhIII atom in both the complexes is uniformly trans-RhN₄Cl₂.     

Ruthenium(II) complexes of hybrid 8‐hydroxyquinoline–thiosemicarbazone ligands: synthesis,characterization and catalytic applications

A series of new hexa‐coordinated ruthenium(II) hydroxyquinoline–thiosemicarbazone complexes of the type [Ru(CO)(EPh₃)(B)(L)] (E = P or As; B = PPh₃, AsPh₃ or Py; L = hydroxyquinoline–thiosemicarbazone) were synthesized by reacting ruthenium precursor complexes [RuHCl(CO)(EPh₃)₂(B)] (E = P or As; B = PPh₃, AsPh₃ or Py) with hydroxyquinoline–thiosemicarbazone ligands in ethanol. The new complexes were characterized by analytical and spectroscopic (FT‐IR, UV–visible, NMR (¹H, ¹³C and ³¹P) and fast atom bombardment (FAB)–mass spectrometric methods. Based on the spectral results, an octahedral geometry was assigned for all the complexes. The new complexes showed good catalytic activity for the conversion of aldehydes to amides in the presence of hydroxylamine hydrochloride–sodium bicarbonate and for the oxidation of alkanes into their corresponding alcohols and ketones in the presence of m‐chloroperbenzoic acid. The complexes also catalyzed the N‐alkylation of benzylamine in the presence of KOtBu in alcohol medium. Copyright © 2013 John Wiley & Sons, Ltd.     

Reactivity of [Mo(NHNRPh)(NNRPh)(acac)X2] (R=Ph,Me; X=Br,I) toward tertiary phosphines

The reactivity of mixed [organohydrazido(1-)][organohydrazido(2-)]molybdenum(VI) complexes [Mo(NHNRPh)(NNRPh)(acac)X₂] {R?=?Ph, X?=?Br (1); R?=?Ph, X?=?I (2) and R?=?Me; X?=?I (3)} with tertiary phosphines as PPh₃, PMePh₂ and PMe₂Ph are examined. The syntheses of [Mo(NNPh₂)₂Br₂(PPh₃)] (4), [Mo(NNPh₂)₂Br₂(PMePh₂)₂] (5), [Mo(NNPh₂)₂Br₂(PMe₂Ph)₂] (6), [Mo(NNPh₂)₂(acac)I(PPh₃)] (7), [Mo(NNPh₂)₂(acac)(PMePh₂)₂]⁺I^? (8) and [Mo(NNMePh)₂(acac)(PMePh₂)₂]⁺I^? (9) are reported. All complexes were characterized by elemental analysis, UV-visible, IR, ¹H and ³¹P{H} NMR spectroscopy.     

Bond stretching and redox behavior in coinage metal complexes of the dichalcogenide dianions [(SPh2P)2CEEC(PPh2S)2]2- (E=S, Se): diradical character of the dinuclear copper(I) complex (E=S)

The metathetical reactions of a) [Li(tmeda)]₂[(S)C(PPh₂S)₂] (Li₂? 3 c ) with CuCl₂ and b) [Li(tmeda)]₂[(SPh₂P)₂CSSC(PPh₂S)₂] (Li₂? 4 c ) with two equivalents of CuCl both afford the binuclear Cu^I complex {Cu₂[(SPh₂P)₂CSSC(PPh₂S)₂]} ( 5 c ). The elongated (C)S? S(C) bond (ca. 2.54 and 2.72 Å) of the dianionic ligand observed in the solid‐state structure of 5 c indicate the presence of diradical character as supported by theoretical analyses. The treatment of [Li(tmeda)]₂[(SPh₂P)₂CSeSeC(PPh₂S)₂] (Li₂? 4 b ) and Li₂? 4 c with AgOSO₂CF₃ produce the analogous Ag^I derivatives, {Ag₂[(SPh₂P)₂CEEC(PPh₂S)₂]} ( 6 b , E=Se; 6 c , E=S), respectively. The diselenide complex 6 b exhibits notably weaker Ag? Se(C) bonds than the corresponding contacts in the Cu^I congeners, and the ³¹P NMR data suggest a possible isomerization in solution. In contrast to the metathesis observed for Cu^I and Ag^I reagents, the reactions of Li₂? 4 b and Li₂? 4 c with Au(CO)Cl involve a redox process in which the dimeric dichalcogenide ligands are reduced to the corresponding monomeric dianions, [(E)C(PPh₂S)₂]^2? ( 3 b , E=Se; 3 c , E=S), and one of the gold centers is oxidized to generate the mixed‐valent Au^I/Au^III complexes, {Au[(E)C(PPh₂S)₂]}₂ ( 7 b , E=Se; 7 c , E=S), with relatively strong aurophilic Au^I???Au^III interactions. The new compounds 5 c , 6 b , c and 7 b , c are characterized in solution by NMR spectroscopy and in the solid state by X‐ray crystallography ( 5 c , 6 b , 7 b and 7 c ) and by Raman spectroscopy ( 5 c and 6 c ). The UV‐visible spectra of coinage metal complexes of the type 5 , 6 and 7 are discussed in the light of results from theoretical analyses using time‐dependent density functional theory.     

Taming Tin(IV) Polyazides

The first charge‐neutral Lewis base adducts of tin(IV) tetraazide, [Sn(N₃)₄(bpy)], [Sn(N₃)₄(phen)] and [Sn(N₃)₄(py)₂], and the salt bis{bis(triphenylphosphine)iminium} hexa(azido)stannate [(PPN)₂Sn(N₃)₆] (bpy = 2,2′‐bipyridine; phen = 1,10‐phenanthroline; py = pyridine; PPN = N(PPh₃)₂) have been prepared using covalent or ionic azide‐transfer reagents and ligand‐exchange reactions. The azides were isolated on the 0.3 to 1 g scale and characterized by IR and NMR spectroscopies, microanalytical and thermal methods and their molecular structures determined by single‐crystal XRD. All complexes have a distorted octahedral Sn[N]₆ coordination geometry and possess greater thermal stability than their Si and Ge homologues. The nitrogen content of the adducts of up to 44 % exceed any Sn^IV compound known hitherto.