155175-65-8

Basic information

• Product Name: trans-[bis(triisopropylphosphine)(chloro)(C(O)CHPh₂CCSiMe₃)rhodium(I)]
• CAS NO: 155175-65-8
• Molecular Weight: 751.29
• Mol File: 155175-65-8.mol

Chemical Properties

• CAS DataBase Reference: trans-[bis(triisopropylphosphine)(chloro)(C(O)CHPh₂CCSiMe₃)rhodium(I)](CAS DataBase Reference)
• NIST Chemistry Reference: trans-[bis(triisopropylphosphine)(chloro)(C(O)CHPh₂CCSiMe₃)rhodium(I)](155175-65-8)
• EPA Substance Registry System: trans-[bis(triisopropylphosphine)(chloro)(C(O)CHPh₂CCSiMe₃)rhodium(I)](155175-65-8)

Safety Data

• Hazardous Substances Data: 155175-65-8(Hazardous Substances Data)

Upstream product

• 88000-15-1 RhCl(triisopropylphosphane)2 
• 71451-02-0 1,1-Diphenyl-4-trimethylsilanyl-but-3-yn-2-one 

Relevant articles and documents

Reactions of alkynylsilanes with [RhCl(PiPr3)2]: The synthesis of four-coordinate (alkyne)-, alkynyl-, and vinylidenerhodium(I) and five- and six-coordinate alkynylhydridorhodium(III) complexes from RC≡CSiMe3, Me3SiC≡CSiMe3, and HC≡CSiMe3

Treatment of [RhCl(PiPr3)2] (1) with the alkynylsilanes RC≡CSiMe3 leads to the formation of the alkyne complexes trans-[RhCl(RC≡CSiMe3)(PiPr3)2] (R = Me (2), Ph (3), CO2Et (4), CO2SiMe3 (5), CH2OH (6), C(O)CHPh2 (7)) or the corresponding vinylidenerhodium(I) derivatives trans-[RhCl(=C=C(SiMe3)R)(PiPr3)2] (R = SiMe3 (8), nPr (9), nBu (10), tBu (11)). Compounds 2-5 rearrange either thermally or photochemically to give the isomeric rhodium vinylidenes 12-15. Whereas the reaction of 1 with HMe2SiC≡CSiMe2H affords the dinuclear hydrido(silyl)rhodium(III) complex [{RhHCl(PiPr3)2}2(μ-Me 2SiC≡CSiMe2)] (16), the five-coordinate alkynylhydrido compound [RhH(C≡CSiMe3)Cl(PiPr3)2] (18) is obtained from 1 and HC≡CSiMe3. 18 rearranges smoothly to yield trans-[RhCl(=C=CHSiMe3)(PiPr3)2] (19), and it reacts with pyridine to give [RhH(C≡CSiMe3)Cl(py)(PiPr3)2] (20). Treatment of 20 with Na[N(SiMe3)2] as a strong hase affords the square-planar alkynyl derivative trans-[Rh(C≡CSiMe3)(py)(PiPr3)2] (21). The corresponding ethene complex trans-[Rh(C≡CSiMe3)(C2H4)(PiPr 3)2] (22) is similarly obtained from 18 and Na[N(SiMe3)2] under a C2H4 atmosphere. The Rh-C2H4 bond in 22 is rather labile and therefore displacement reactions with alkynes occur readily. With HC≡CSiMe3, the bis(alkynyl)hydridorhodium(III) compounds [RhH(C≡CSiMe3)2(PiPr3)2] (23) and [RhH(C≡CSiMe3)2(py)(PiPr3)2] (24) and with RC≡CSiMe3 the alkyne(alkynyl)rhodium(I) derivatives trans-[Rh(C≡CSiMe3)(RC≡CSiMe3)(PiPr 3)2] (R = CO2Et (25), CO2SiMe3 (26)) are obtained. The X-ray crystal structure of 24 (orthorhombic, space group Pna21 (No. 33) with a = 19.109(7) A?, b = 17.397(4) A?, c = 12.329(3) A?, and Z = 4) reveals a trans disposition of the two alkynyl, the two phosphine, and the hydride and the pyridine units. The synthesis of some cyclopentadienylrhodium complexes containing alkynylsilane ligands will also be described.