Synthesis of [TpRu(CO)(PPh3)]2(μ-CHCHCHCHC6H4CHCHCHCH) from Wittig reactions

Treatment of [Ru(CHCHCH₂PPh₃)X(CO)(PPh₃)₂]⁺ (X=Cl, Br) with KTp (Tp=hydridotris(pyrazolyl)borate) and NaBPh₄ produced [TpRu(CHCHCH₂PPh₃)(CO)(PPh₃)]BPh₄. Reaction of RuHCl(CO)(PPh₃)₃ with HCCCH(OEt)₂ produced Ru(CHCHCH(OEt)₂)Cl(CO)(PPh₃)₂, which reacted with KTp to give TpRu(CHCHCHO)(CO)(PPh₃). Treatment of [TpRu(CHCHCH₂PPh₃)(CO)(PPh₃)]BPh₄ with NaN(SiMe₃)₂ and benzaldehyde produced TpRu(CHCHCHCHPh)(CO)(PPh₃). The later complex was also produced when TpRu(CHCHCHO)(CO)(PPh₃) was treated with PhCH₂PPh₃Cl/NaN(SiMe₃)₂. The bimetallic complex [TpRu(CO)(PPh₃)]₂(μ-CHCHCHCHC₆H₄CHCHCHCH) was obtained from the reaction of [TpRu(CHCHCH₂PPh₃)(CO)(PPh₃)]BPh₄ with NaN(SiMe₃)₂ and terephthaldicarboxaldehyde.     

Preparation and reactivity of osmium(II) hydride complexes with phosphites and polypyridyls

Chloro-complexes [OsCl(N-N)P₃]BPh₄ (1, 2) [N-N=2,2^′-bipyridine (bpy) and 1,10-phenanthroline (phen); P=P(OEt)₃ and PPh(OEt)₂] were prepared by allowing OsCl₄(N-N) to react with zinc dust in the presence of phosphites. Treatment of the chloro-complexes 1, 2 with NaBH₄ yielded, in the case of bpy, the hydride [OsH(bpy)P₃]BPh₄ (4) derivatives. Mono-phosphite [OsCl(bpy)₂P]BPh₄ (3) complexes were also prepared by reacting the [OsCl₂(bpy)₂]Cl compound with zinc dust in the presence of phosphite. Protonation reaction of the hydride [OsH(bpy)P₃]⁺ (4) cations with Brønsted acid was studied and led to thermally unstable (above 0 °C) dihydrogen [Os(η²-H₂)(bpy)P₃]²⁺ (4*) derivatives. The presence of the H₂ ligand is supported by variable-temperature NMR spectra and T_1min measurements. Carbonyl [Os(CO)(bpy){P(OEt)₃}₃](BPh₄)₂ (5), nitrile [Os(CH₃CN)(bpy){P(OEt)₃}₃](BPh₄)₂ (6), and hydrazine [Os(bpy)(NH₂NH₂){P(OEt)₃}₃](BPh₄)₂ (7) complexes were prepared by substituting the H₂ ligand in the η²-H₂ (4*) derivatives. Aryldiazene complex [Os(C₆H₅NNH)(bpy){P(OEt)₃}₃](BPh₄)₂ (8) was also obtained by allowing the hydride [OsH(bpy)P₃]BPh₄ to react with phenyldiazonium cation.     

Reactions of IrHCl2(PPh3)2{P(OEt)3} with Organic Azides: Formation of Aminophosphonium Salts

Aminophosphonium salts [Ph₃PN(H)R]BPh₄ ( 1 ) [R = C₆H₅CH₂ ( 1a ), 4‐CH₃C₆H₄CH₂ ( 1b ), C₆H₅ ( 1c )] were obtained by allowing hydride IrHCl₂(PPh₃)₂{P(OEt)₃} to react first with triflic acid and then with the organic azide RN₃. The compounds were characterized spectroscopically and by X‐ray crystal structure determination of [Ph₃PN(H)CH₂C₆H₄‐4‐CH₃]BPh₄ ( 1b ). A reaction path for the formation of aminophosphonium cations is also proposed.     

E/Z isomerism in monoalkylated derivatives of [Pt2(µ-S)2(PPh3)4] containing 2,4-dinitrophenylhydrazone substituents

Alkylation of [Pt₂(µ-S)₂(PPh₃)₄] with 2,4-dinitrophenylhydrazone-functionalized alkylating agents XC₆H₄C{=NNHC₆H₃(NO₂)₂}CH₂Br (X?=?H, Ph) gives monoalkylated cations [Pt₂(µ-S){µ-SCH₂C{=NNHC₆H₃(NO₂)₂}C₆H₄X}(PPh₃)₄]⁺. An X-ray diffraction study on [Pt₂(µ-S){µ-SCH₂C{=NNHC₆H₃(NO₂)₂}Ph}(PPh₃)₄]BPh₄ shows the crystal to be the Z isomer, with the phenyl ring and NHC₆H₃(NO₂)₂ groups mutually trans. ¹H- and ³¹P{¹H} NMR spectroscopic methods indicate a mixture of Z (major) and E (minor) isomers in solution, which slowly convert mainly to the E isomer. Reaction of [Pt₂(µ-S)₂(PPh₃)₄] with the dinitrophenylhydrazone of chloroacetone [ClCH₂C{=NNH(C₆H₃(NO₂)₂}Me] and NaBPh₄ gives [Pt₂(µ-S){µ-SCH₂C{=NNHC₆H₃(NO₂)₂}Me}(PPh₃)₄]BPh₄, which exists as a single (E) isomer.     

Palladium and platinum catalyzed hydroselenation of alkynes: SeH vs SeSe addition to CC bond

A mechanistic study of the hydroselenation of alkynes catalyzed by Pd(PPh₃)₄ and Pt(PPh₃)₄ has shown that the palladium complex gives products of both SeH and SeSe bond addition to the triple bond of alkynes, while the platinum complex selectively catalyzes SeH bond addition. The key intermediate of PhSeH addition to the metal center, namely Pt(H)(SePh)(PPh₃)₂, was detected by ¹H-NMR spectroscopy. The analogous palladium complex rapidly decomposes with evolution of molecular hydrogen. A convenient method was developed for the preparation of Markovnikov hydroselenation products H₂CC(SePh)R, and the scope of this reaction was investigated. The first X-ray structure of the Markovnikov product H₂CC(SePh)CH₂N⁺HMe₂·HOOCCOO⁻ is reported.     

Interconversion of Metallabenzenes and Cyclic η2‐Allene‐Coordinated Complexes

Treatment of the osmabenzene [Os{CHC(PPh₃)CHC(PPh₃)CH} Cl₂(PPh₃)₂]Cl ( 1 ) with excess 8‐hydroxyquinoline produces monosubstituted osmabenzene [Os{CH C(PPh₃) CHC(PPh₃)CH}(C₉H₆NO)Cl(PPh₃)]Cl ( 2 ) or disubstituted osmabenzene [Os{CHC(PPh₃)CHC(PPh₃)CH} (C₉H₆NO)₂]Cl ( 3 ) under different reaction conditions. Osmabenzene 2 evolves into cyclic η²‐allene‐coordinated complex [Os{CH?C(PPh₃)CH=(η²‐C?CH₂)}(C₉H₆NO)(PPh₃)₂]Cl ( 4 ) in the presence of excess PPh₃ and NaOH, presumably involving a P? C bond cleavage of the metallacycle. Reaction of 4 with excess 8‐hydroxyquinoline under air affords the S_NAr product [(C₉H₆NO)Os{CHC(PPh₃)CHCHC} (C₉H₆NO)(PPh₃)]Cl ( 5 ). Complex 4 is fairly reactive to a nucleophile in the presence of acid, which could react with water to give carbonyl complex [Os{CH?C(PPh₃)CH?CH₂}(C₉H₆NO) (CO)(PPh₃)₂]Cl ( 6 ). Complex 4 also reacts with PPh₃ in the presence of acid and results in a transformation to [Os {CHC(PPh₃)CHCHC}(C₉H₆NO)Cl (PPh₃)₂]Cl ( 7 ) and [Os{CH?C(PPh₃) CH=(η²‐C?CH(PPh₃))}(C₉H₆NO) Cl(PPh₃)]Cl ( 8 ). Further investigation shows that the ratio of 7 and 8 is highly dependent on the amount of the acid in the reaction.     

Preparation and reactivity with azo-species of hydride and dihydrogen complexes of osmium stabilised by tris(pyrazolyl)borate and phosphite ligands

Mixed-ligand OsCl(Tp)L(PPh₃) complexes 1 [Tp = hydridotris(pyrazolyl)borate; L = P(OMe)₃, P(OEt)₃ and PPh(OEt)₂] were prepared by allowing OsCl(Tp)(PPh₃)₂ to react with an excess of phosphite. Treatment of chlorocomplexes 1 with NaBH₄ in ethanol afforded hydride OsH(Tp)L(PPh₃) derivatives 2. Stable dihydrogen [Os(η²-H₂)(Tp)L(PPh₃)]BPh₄ derivatives 3 were prepared by protonation of hydrides 2 with HBF₄ · Et₂O at −80 °C. The presence of the η²-H₂ ligand is supported by short T_1 min values and J_HD measurements on the partially deuterated derivatives. Treatment of the hydride OsH(Tp)[P(OEt)₃](PPh₃) complex with the aryldiazonium salt [4-CH₃C₆H₄N₂]BF₄ afforded aryldiazene [Os(4-CH₃C₆H₄NNH)(Tp){P(OEt)₃}(PPh₃)]BPh₄ derivative 4. Instead, aryldiazenido [Os(4-CH₃C₆H₄N₂)(Tp)[P(OEt)₃](PPh₃)](BF₄)₂ derivative 5 was obtained by reacting the hydride OsH(Tp)[P(OEt)₃](PPh₃) first with methyltriflate and then with aryldiazonium [4-CH₃C₆H₄N₂]BF₄ salt. Spectroscopic characterisation (IR, ¹⁵N NMR) by the ¹⁵N-labelled derivative strongly supports the presence of a near-linear Os-NN-Ar aryldiazenido group. Imine [Os{η¹-NHC(H)Ar}(Tp){P(OEt)₃}(PPh₃)]BPh₄ complexes 6 and 7 (Ar = C₆H₅, 4-CH₃C₆H₄) were also prepared by allowing the hydride OsH(Tp)[P(OEt)₃](PPh₃) to react first with methyltriflate and then with alkylazides.     

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.     

[RhCl(CO)(PPh3)]2. A precursor for the synthesis of cationic rhodium complexes with nitrogen donor ligands

Summary The use of [RhCl(CO)(PPh₃)]₂ as a precursor for the synthesis of complexes of the types [Rh(CO)L₂(PPh₃)]A (A = [ClO₄]^– or [BPh₄]^–; L = pyridine type ligand) and [Rh(CO)(L-L)(PPh₃)]A (A = [ClO₄]^– or [BPh₄]^–; L-L = bidentate nitrogen donor) and the preparation of several complexes of the types [Rh(CO)L(PPh₃){P(p-RC₆H₄)₃}]BPh₄ and [Rh(CO)(phen)(PPh₃){P(p-RC₆H₄)₃}]A (A = [ClO₄]^– or [BPh₄]^–; R = H or Me) is described.Author to whom all correspondence should be directed.     

Reactivity with Amines of Bis(cyanamide) and Bis(cyanoguanidine) Complexes of the Iron Triad

Treatment of bis(cyanamide) [M(N≡CNEt₂)₂L₄](BPh₄)₂ and bis(cyanoguanidine) [M{N≡CN(H)C(NH₂)=NH}₂L₄](BPh₄)₂ complexes [M = Fe, Ru, Os; L = P(OEt)₃] with an excess of amine RNH₂ (R = nPr, iPr) affords mixed‐ligand complexes with cyanamide and amine [M(NH₂R)(N≡CNEt₂)L₄](BPh₄)₂ ( 1a – 5a ) and [M(NH₂R){N≡CN(H)C(NH₂)=NH}L₄](BPh₄)₂ ( 1b , 2b ). The complexes were characterized by spectroscopy and X‐ray crystal structure determination of [M(NH₂iPr)(N≡CNEt₂){P(OEt)₃}₄](BPh₄)₂ [M = Ru ( 3a ), Os ( 5a )].     

The Reactions of Two New Alkoxy-silyl Functionalized Alkynes with M<Subscript>3</Subscript>(CO)<Subscript>12</Subscript> {M = Fe,Ru} and Co<Subscript>2</Subscript>(CO)<Subscript>8</Subscript>. Spectroscopic Identification of the Products

The new alkoxysilyl-functionalized alkynes [HC≡CCH₂N(H)C(=O)N(H)(CH₂)₃Si(OEt)₃] and [HC≡C(C₆H₄)–N(H)C(=O)N(H)(CH₂)₃Si(OEt)₃] have been synthesized using literature methods. These have been reacted with Fe₃(CO)₁₂, Ru₃(CO)₁₂ and Co₂(CO)₈. With the iron carbonyl only decomposition was observed: with Ru₃(CO)₁₂ splitting of the alkynes into their parent components and formation of the complexes (μ-H)Ru₃(CO)₉[HC=N(CH₂)₃Si(OEt)₃], (μ-H)Ru₃(CO)₉[C–C(C₆H₄)NH₂] and (μ-H)₂Ru₃(CO)₉[HC–CCH₃] occurred. Finally, with Co₂(CO)₈ formation of complexes Co₂(CO)₆(HC₂R) R=(C₆H₄)NH₂, CH₂NH(CO)NH(CH₂)₃Si(OEt)₃, (C₆H₄)NH(CO)NH(CH₂)₃Si(OEt)₃ containing the intact alkynes could be obtained.     

Ruthenium bidentate phosphine complexes for the coordination and catalytic dehydrogenation of amine- and phosphine-boranes

Addition of the amine–boranes H₃B ? NH₂tBu, H₃B ? NHMe₂ and H₃B ? NH₃ to the cationic ruthenium fragment [Ru(xantphos)(PPh₃)(OH₂)H][BAr^F₄] ( 2 ; xantphos=4,5‐bis(diphenylphosphino)‐9,9‐dimethylxanthene; BAr^F₄=[B{3,5‐(CF₃)₂C₆H₃}₄]^?) affords the η¹‐B? H bound amine–borane complexes [Ru(xantphos)(PPh₃)(H₃B ? NH₂tBu)H][BAr^F₄] ( 5 ), [Ru(xantphos)(PPh₃)(H₃B ? NHMe₂)H][BAr^F₄] ( 6 ) and [Ru(xantphos)(PPh₃)(H₃B ? NH₃)H][BAr^F₄] ( 7 ). The X‐ray crystal structures of 5 and 7 have been determined with [BAr^F₄] and [BPh₄] anions, respectively. Treatment of 2 with H₃B ? PHPh₂ resulted in quite different behaviour, with cleavage of the B? P interaction taking place to generate the structurally characterised bis‐secondary phosphine complex [Ru(xantphos)(PHPh₂)₂H][BPh₄] ( 9 ). The xantphos complexes 2 , 5 and 9 proved to be poor precursors for the catalytic dehydrogenation of H₃B ? NHMe₂. While the dppf species (dppf=1,1′‐bis(diphenylphosphino)ferrocene) [Ru(dppf)(PPh₃)HCl] ( 3 ) and [Ru(dppf)(η⁶‐C₆H₅PPh₂)H][BAr^F₄] ( 4 ) showed better, but still moderate activity, the agostic‐stabilised N‐heterocyclic carbene derivative [Ru(dppf)(ICy)HCl] ( 12 ; ICy=1,3‐dicyclohexylimidazol‐2‐ylidene) proved to be the most efficient catalyst with a turnover number of 76 h^?1 at room temperature.     

New nitrosyl(perfluorocarboxylato) complexes of the platinum metals

Perfluorocarboxylic acids (R_FCOOH) (R_F = CF₃,C₂F₅ and (for Rh) C₆F₅) react with the species [M(NO)₂(PPh₃)₂] (M = Ru, Os) and [M′(NO)(PPh₃)₃] (M′ = Rh, Ir) to yield new nitrosyl complexes [Ru(OCOR_F)₃(NO)(PPh₃)₂], [OsH(OCOR_F)₂(NO)(PPh₃)₂], [Os(OCOR_F)(NO)₂(PPh₃)₂][OCOR_F], [Ir(OCOR_F)(NO)(PPh₃)₂][OCOR_F] and [Rh(OCOR_F)₂(NO)(PPh₃)₂].     

Reactivity of cationic methyl rhodium(III) complexes cis-[Rh(β-diket)(PPh3)2(CH3)(CH3CN)][BPh4] toward ligands of different character: pyridine, carbon monoxide, and triphenylphosphine

Cationic methyl complex of rhodium(III), cis-[Rh(Acac)(PPh₃)₂(CH₃)(Py)][BPh₄] (1) as a single isomer with Py in the trans to PPh₃ position, is formed upon the reaction of cis-[Rh(Acac)(PPh₃)₂(CH₃)(CH₃CN)][BPh₄] with pyridine in methylene chloride solution.Complex 1 was characterized by elemental analysis and by ³¹P{¹H} and ¹H NMR spectra.Cationic pentacoordinate acetyl complexes, trans-[Rh(Acac)(PPh₃)₂(COCH₃)][BPh₄] (2) and trans-[Rh(BA)(PPh₃)₂(COCH₃)][BPh₄] (3), are prepared by action of carbon monoxide on cis-[Rh(Acac)(PPh₃)₂(CH₃)(CH₃CN)][BPh₄] and cis-[Rh(BA)(PPh₃)₂(CH₃)(CH₃CN)][BPh₄], respectively, in methylene chloride solutions.Complexes 2 and 3 were characterized by elemental analysis and by IR, ³¹P{¹H}, ¹³C{¹H} and ¹H NMR. According to NMR data, 2 and 3 in solution are non-fluxional trigonal bipyramids with β-diketonate and acetyl ligands in the equatorial plane and axial phosphines.In solutions, 2 and 3 gradually isomerize into octahedral methyl carbonyl complexes trans-[Rh(Acac)(PPh₃)₂(CO)(CH₃)][BPh₄] (4) and trans-[Rh(BA)(PPh₃)₂(CO)(CH₃)][BPh₄] (5), respectively.Complexes 4 and 5 were characterized by IR, ³¹P{¹H}, ¹³C{¹H} and ¹H NMR, without isolation.Upon the action of PPh₃ on cis-[Rh(Acac)(PPh₃)₂(CH₃)(CH₃CN)][BPh₄] and cis-[Rh(BA)(PPh₃)₂(CH₃)(CH₃CN)] [BPh₄], reductive elimination of the methyl ligand as a phosphonium salt, [CH₃PPh₃][BPh₄], occurs to give square planar rhodium(I) complexes [Rh(Acac)(PPh₃)₂] and[Rh(BA)(PPh₃)₂], respectively. The reaction products were identified in the reaction mixtures by ³¹P{¹H} and ¹H NMR.     

Übergangsmetall—methylen-komplexe : XXXIV. Aufbau alicyclischer methylen-brucken nach einem modifizierten diazoalkan-verfahren

The mixed dinitrogen-isocyanide complexes mer-[ReCl(N₂)(CNMe)-{P(OMe)₃}₃] (I) and [ReCl(N₂)(CNMe)(PPh₃) {P(OEt)₃}₂] (II) are obtained by a novel route through reactions of CNMe with the organodiazenido species [ReCl₂(NNCOPh) {P(OMe)₃ }₃] and [ReCl₂(NNCOPh)(PPh₃){P(OEt)₃ }₂] (III, newly synthesized), whereas mer-[ReCl(N₂)(PPh₃) {P(OMe)₃ }₃] (IV) (which gives I by reaction with CNMe) is formed in the reaction of [$\text{ReCl}{}_2\text{(NNC}$OPh)(PPh₃)₂] with P(OMe)₃; the structure of complex I is authenticated by X-ray analysis.     

Nucleophilic addition of water to coordinated dipyridylethylene in rhenium(V) complexes

Complexes of general formula [ReOX₂{(C₅H₄N)CH(O)CH₂(C₅H₄N)}] (X?=?Cl,?I) were prepared by reaction of trans-[ReOCl₃(PPh₃)₂] and trans-[ReOI₂(OEt)(PPh₃)₂] with cis-1,2-di-(2-pyridyl)ethylene (DPE) in ethanol and benzene in air. The coordinated DPE ligand undergoes addition of water at the ethylenic carbon atoms, and the (C₅H₄N)CH(O)CH₂(C₅H₄N) moiety acts as a uninegative terdentate N,O,N-donor ligand. X-ray crystal structures of both complexes have been determined and show distorted octahedral geometry at the rhenium(V) centre.     

Transition metal (Group 6, Ru and Group 10) derivatives of aminophosphines, Ph2PN(H)R (R=Ph, C6H11)

The reactions of aminophosphines with Group 6 metal carbonyls afford both mono-substituted and disubstituted complexes. The reaction of Ph₂PN(H)C₆H₁₁ with molybdenum tetracarbonyl derivative gives a mixture of cis and trans-isomers. The reaction of Ph₂PN(H)Ph with Pd(COD)Cl₂ leads to the PN bond cleavage to give chloro bridged dimer, [Pd(PPh₂O)(PPh₂OH)(μ-Cl)]₂, whereas with Pt(COD)Cl₂, disubstituted cis-[PtCl₂{PPh₂N(H)R}₂]₂ was obtained. The reaction of Ph₂PN(H)C₆H₁₁ with RuCl₂(DMSO)₄ or RuCl₂(PPh₃)₃ leads to the formation of ionic complex, [RuCl{Ph₂PN(H)C₆H₁₁}₃]Cl.     

Alkylation of [Pt2(μ-S)2(PPh3)4] with boronic acid derivatives

The reactivity of the metalloligand [Pt₂(μ-S)₂(PPh₃)₄] with the boron-functionalized alkylating agents BrCH₂(C₆H₄)B(OR)₂ (R = H or C(CH₃)₂) was investigated by electrospray ionization mass spectrometry (ESI-MS) in real time using pressurized sample infusion (PSI). The macroscopic reaction of [Pt₂(μ-S)₂(PPh₃)₄] with one mole equivalent of alkylating agents BrCH₂(C₆H₄)B{OC(CH₃)₂}₂ and BrCH₂(C₆H₄)B(OH)₂ gave the dinuclear monocationic μ-sulfide thiolate complexes [Pt₂(μ-S){μ-SCH₂(C₆H₄)B{OC(CH₃)₂}₂}(PPh₃)₄]⁺ and [Pt₂(μ-S){μ-S⁺CH₂(C₆H₄)B(OH)(O^?)}(PPh₃)₄]. The products were isolated as the [PF₆]^? salt and zwitterion, respectively, and fully characterized by ESI-MS, IR, ¹H and ³¹P NMR spectroscopy, and single-crystal X-ray structure determinations.     

The reaction of trihydrobistriphenylphosphine iridium IrH3(PPh3)2 with diazonium salts

The reaction of IrH₃(PPh₃)₂ with p-substituted aryldiazonium salts gives the compounds [IrH₂(NHNC₆H₄R)(PPh₃)₂]⁺BF₄^- at low temperature (-10°C) and the o-metalated complexes [I$\text{rH(NHN}$C₆H₃R)(PPh₃)₂]⁺BF₄^- (R  F, OCH₃) at 40–50°C. The reactions of the o-metalated complexes with CO, PPh₃, NaI and HCl have been studied.     

The reactions of 2-benzoylpyridine with [RuHCl(CO)(PPh3)3] and [(C6H6)RuCl2]2

The reactions of [RuHCl(CO)(PPh₃)₃] and [(C₆H₆)RuCl₂]₂ with 2-benzoylpyridine have been examined, and two novel ruthenium(II) complexes – [RuCl(CO)(PPh₃)₂(C₅H₄NCOO)] and [RuCl₂(C₁₂H₉NO)₂] – have been obtained. The compounds have been studied by IR and UV–Vis spectroscopy, and X-ray crystallography. The molecular orbital diagrams of the complexes have been calculated with the density functional theory (DFT) method. The spin-allowed singlet–singlet electronic transitions of the compounds have been calculated with the time-dependent DFT method, and the UV–Vis spectra of the compounds have been discussed on this basis.