Carbonyl Halide, and Related Complexes

Hayakawa, H. Nakayama, A. Kobayashi, and Y. Sasaki, Bull. Chem. Soc. Japan, 1978, 51, 2041. 

Thiollet, R. Poilblanc, D. Voigt, and F. Mathey, Inorg. Chim. Acta, 1978, 30, L294 

Photolysis of Re2(CO)io with the phosphinic acids RgP02H (R=Me or Ph) in the donor solvents THF or dioxan (L) gives the polymeric complexes [Re-(C0)3( M-02PR2)L]w. Substitution of L in these complexes by CO yields dimeric [Re(C0)4(02PR2)l2, whereas elimination of L affords polymeric [Re(CO)3-(02PR2 ]n, and reaction with dppe gives [Re(CO)3(OaPRa)(dppe)].  

The crystal and molecular structures of [Re2(CO)6(/i-Br)2C -Ph2PPPh2)], [Rea(CO)6(/ -Br)2(A -MeSSMe)], and [Re2(CO)60-Br)2(THF)2] have been elucidated. The latter compound reacts with neutral donors to give yhc-[Re(CO)3-BrLg] (L = PPh2Cl, PPhaH, or MeaNH L2 = en, bipy, or phen) complexes, and with [EtaNCSa] in the presence of EtaNH to give [Re(CO)3(SaCNEt2)-(NHEta)].  

Carbonyl, Carbonyl Halide, and Related Complexes.— The Rea(CO)io-PPh3 reaction, previously held to yield paramagnetic products such as (Re(CO)3-(PPh3)a], in fact produces mainly f//axw/-[Re2(CO)8(PPh3)2] and mer-trans- 

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Carbonyl/ Carbonyl Halide and. Related- Complexes.- The photochemical disproportionation of Mn2 ICO) in the presence of the nitrogen donors py, NEt and dien occurs by a radical chain pathway,the key step being the formation of 19-electron inter-... 

Carbonyl, Carbonyl Halide and Related Complexes.— The photochemistry of N2(C0) q (M = Mn or Re) has been investigated by laser flash photolysis. Two primary photoprocesses are observed metal-metal bond cleavage producing M(CO) radicals, cuid carbonyl... 

A list of the reported ionic heptacoordinate halide carbonyl cations and related complexes is presented in Table I. 

Carbonyl. Carbonvl Halide, and Related Complexes.—Reaction... 

Metal cluster compounds can be conveniently grouped into two classes (I) polynuclear carbonyls, nitrosyls. and related compounds and (II) halide and oxide complexes. The former group was included m Chapter 15. The second class will be discussed in this section.146... 

Mctallocarboranes, Ten Years of, 14, 145 Methyltin Halides and Their Molecular Complexes, 14, 63 Nitrogen Groups in Metal Carbonyl and Related Complexes, 10, 115 Nitrosyls, 7, 211... 

Since Wakamatsu serendipitously discovered amidocarbonylation while performing the cobalt-catalyzed hydroformyla-tion of olefins in 1971, this unique carbonylation reaction, affording a-amino acids directly from aldehydes, has been extensively studied.More recently, palladium-catalyzed processes have been developed to expand the scope of this reaction.The Pd-catalyzed amidocarbonylation has been applied to aldehydes,aryl halides, and imines. As a related reaction, lactamization " of aryl halides catalyzed by a rhodium complex has also been developed. 

Many transition metal carbonyl complexes have been prepared, often inadvertently, by allowing a metal halide or polyhalometallate to react with a ligand in an organic solvent with carbon-oxygen bonds. Indeed, carbonyl abstraction is an important synthetic route to tran5 -[MCl(CO)(PPh3)2] (M = Rh, Ir) or [OsHX(CO)(ZPh3)3] (X = Cl, Br Z = P, As) and related osmium(II) complexes. 

The lanthanide halides are usually bi(cyclopentadienyl) and related lanthanide complexes M is an alkali metal or silver, and A is an anionic transition metal carbonyl compound or tetraphenyl borate. The formation of the insoluble salt MX is a driving force for this reaction. 

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