Five- and Six-Coordinate Bis(alkynyl)rhodium(III) Complexes Containing a Rh−SnPh<sub>3</sub> Bond

The synthesis of [MePPh 3 ][SnCB 10 H 11 ] is presented together with its structural, NMR, and 119 Sn Mo ¨ssbauer spectroscopical characterization. Two transition metal complexes, [Au 4 (PPh 3 ) 4 (SnCB 10 H 11 ) 2 ] and [Bu 4 N] 2 [Rh(PPh 3 ) 2 (SnCB 10 H 11 ) 3 ], with the carbastannaborate coordinated at rhodium or gold via the tin atom are presented, and the structural and NMR spectroscopical data are discussed.

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“…The quadrupole splitting of 1 (C s ) of 2. 33(1) mm‚s -1 reflects the lower site symmetry compared to [SnB 11 H 11 ] 2-(C 5V ) at 1.71 mm‚s -1 .…”

Section: Resultsmentioning

confidence: 99%

1,2-Carbastanna-closo-dodecaborate, a New Tin Ligand in Coordination Chemistry: Synthesis, Structure, and Reactivity

Joosten¹,

Weissinger²,

Kirchmann³

et al. 2007

Organometallics

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“…In contrast to this, the reaction of trans -[IrCl(HC⋮CR)(P i Pr 3 ) 2 ] to give trans -[IrCl(CCHR)(P i Pr 3 ) 2 ] proceeds via the alkynylhydrido complex [IrHCl(C⋮CR)(P i Pr 3 ) 2 ] as an isolable intermediate . In this context it should be noted that we recently described the preparation and structural characterization of the five-coordinate stannylrhodium(III) compound [Rh(SnPh 3 )(C⋮CPh) 2 (P i Pr 3 ) 2 ], which is formed from [Rh(η 2 -O 2 CMe)(P i Pr 3 ) 2 ] and 2 equiv of Ph 3 SnC⋮CPh …”

Section: Resultsmentioning

confidence: 99%

Alkynes and Diynes as Precursors for Organoiridium Complexes Containing Iridium−Carbon Single and Double Bonds^,¹

et al. 1997

Self Cite

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The in situ generated species [IrCl(C8H14)(PiPr3)2] as well as the dihydrido complex [IrH2Cl(PiPr3)2] (15) were found to be quite reactive toward alkynes and diynes with either H or SiMe3 as substituents at the C⋮C and C⋮CC⋮C units. While the thermal or photochemical reaction of [IrCl(C8H14)(PiPr3)2] with Me3SiC⋮CR (R = Ph, Me, nBu, SiMe3, CH2OH, CMe2OSiMe3, CO2Et) led to trans-[IrCl{CC(SiMe3)R}(PiPr3)2] (3−9) for R = CO2Et via the isolated π-alkyne metal intermediate trans-[IrCl(η2-Me3SiC⋮CR)(PiPr3)2] (2), photolysis of 15 in the presence of Me3SiC⋮CC⋮CSiMe3 gave trans-[IrCl{CC(SiMe3)C⋮CSiMe3}(PiPr3)2] (19). Compound 19 was also obtained by thermal or photochemical rearrangement of trans-[IrCl(η2-Me3SiC⋮CC⋮CSiMe3)(PiPr3)2] (18). The dihydrido complex 15 reacted with HC⋮CC⋮CH at −60 °C to yield [{IrHCl(PiPr3)2}2(μ-C⋮CC⋮C)] (16) and with HC⋮CC⋮CSiMe3 to give [IrHCl(C⋮CC⋮CSiMe3)(PiPr3)2] (20), from which the vinylidene isomer trans-[IrCl(CCHC⋮CSiMe3)(PiPr3)2] (22) was generated on heating. The reaction of 15 with propargylic alcohols HC⋮CCR(R‘)OH led to different types of products, depending on the substituents R and R‘. Whereas for R = R‘ = iPr the five-coordinate alkynyl hydrido complex [IrHCl{C⋮CC(iPr)CMe2}(PiPr3)2] (23) was formed, the six-coordinate carbonyl hydrido vinyl derivative [IrHCl{(E)-CHCHPh}(CO)(PiPr3)2] (25) was isolated for R = H and R‘ = Ph. Treatment of 15 with HC⋮CCPh2OH afforded, via [IrHCl(C⋮CCPh2OH)(PiPr3)2] (27) or the isomer trans-[IrCl(CCHCPh2OH)(PiPr3)2] (28), the allenylideneiridium(I) compound trans-[IrCl(CCCPh2)(PiPr3)2] (29) in excellent yield. Hydrogenation of 29 gave the allene complex trans-[IrCl(η2-CH2CCPh2)(PiPr3)2] (30), the structure of which was determined by X-ray crystallography. The substituted vinylideneiridium compound trans-[IrCl{CC(SiMe3)C⋮CCPh2OH}(PiPr3)2] (33) was obtained from [IrCl(C8H14)(PiPr3)2] and Me3SiC⋮CC⋮CCPh2OH via the isomeric π-alkyne complex 32 as isolated intermediate.

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“…Coupling of alkynyl ligands can also occur. For example, bis(alkynyl) complexes of iron(II), osmium(II), or rhodium(III) can lead to coordinated butenynes or butadiynes by oxidative coupling. A diyne trimer is formed from diyne in a reaction induced by [Ru 4 (μ 3 -PPh)(CO) 13 ] …”

Section: Introductionmentioning

confidence: 99%

Heteronuclear Triangular Clusters of the Type [Pt₂M(μ₃-η¹:η¹:η²-PhC⋮CC⋮CPh)(CO)₅(PPh₃)₂] (M = Fe or Ru)

1998

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The 46-electron heteronuclear clusters [Pt2M(μ3-η1:η1:η2-PhC⋮CC⋮CPh)(CO)5(PPh3)2] (M = Fe or Ru) are formed in moderate yield by treating [Pt(η2-PhC⋮CC⋮CPh)(PPh3)2] with [Fe(CO)5] or [Ru3(CO)12] in refluxing toluene. The Pt2Fe and Pt2Ru clusters are isostructural, being composed of two Pt(CO)(PPh3) units and a M(CO)3 group linked by two Pt−Fe or Pt−Ru bonds with the μ3-diyne coordinated through only one C⋮C bond.

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Five- and Six-Coordinate Bis(alkynyl)rhodium(III) Complexes Containing a Rh−SnPh₃ Bond

Cited by 29 publications

References 18 publications

1,2-Carbastanna-closo-dodecaborate, a New Tin Ligand in Coordination Chemistry: Synthesis, Structure, and Reactivity

1,2-Carbastanna-closo-dodecaborate, a New Tin Ligand in Coordination Chemistry: Synthesis, Structure, and Reactivity

Alkynes and Diynes as Precursors for Organoiridium Complexes Containing Iridium−Carbon Single and Double Bonds^,¹

Heteronuclear Triangular Clusters of the Type [Pt₂M(μ₃-η¹:η¹:η²-PhC⋮CC⋮CPh)(CO)₅(PPh₃)₂] (M = Fe or Ru)

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Five- and Six-Coordinate Bis(alkynyl)rhodium(III) Complexes Containing a Rh−SnPh3 Bond

Cited by 29 publications

References 18 publications

1,2-Carbastanna-closo-dodecaborate, a New Tin Ligand in Coordination Chemistry: Synthesis, Structure, and Reactivity

1,2-Carbastanna-closo-dodecaborate, a New Tin Ligand in Coordination Chemistry: Synthesis, Structure, and Reactivity

Alkynes and Diynes as Precursors for Organoiridium Complexes Containing Iridium−Carbon Single and Double Bonds,1

Heteronuclear Triangular Clusters of the Type [Pt2M(μ3-η1:η1:η2-PhC⋮CC⋮CPh)(CO)5(PPh3)2] (M = Fe or Ru)

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Five- and Six-Coordinate Bis(alkynyl)rhodium(III) Complexes Containing a Rh−SnPh₃ Bond

Alkynes and Diynes as Precursors for Organoiridium Complexes Containing Iridium−Carbon Single and Double Bonds^,¹

Heteronuclear Triangular Clusters of the Type [Pt₂M(μ₃-η¹:η¹:η²-PhC⋮CC⋮CPh)(CO)₅(PPh₃)₂] (M = Fe or Ru)