Pd-catalysed carbonyl ligand substitution reactions of [Mn(CO)5Br] and [Re(CO)5Br] by isocyanides

Alkyne Ligand Enhancement of the Substitution Lability of Mononuclear Osmium, Ruthenium, and Iron Carbonyls

“…Other promoters of CO elimination that have been used include R 3 PO, KOMe, KH, and NaBH 4 . Another approach is to use electron-transfer reagents, including supported transition metals, to generate labile 17- or 19-electron species …”

Manganese Nitrosyl and Isonitrile Complexes

“…For example, reaction o f Mn(Cp)(CO) 3 with CNR ( R = Bu\ Bz, Cy, Me, or 2,6-Me 2 C 6 H 3 ) in toluene at reflux to form Mn(Cp)(CO) 2 (CNR) is greatly accelerated in the presence o f PdO, as is substitution at MnBr(CO) 5 in THF at room temperature by a variety o f CNR. 3 It has been known for some time that substitution of Mn(Cp)(CO) 3 , it was concluded t h a t CNCF 3 is the strongest rc-acid among these ligands. 4 Synthesis of the unstable isonitrile CNC 6 F 5 (m.p.…”

“…4 Preparations of Mn(Cp*)(CO)(CNCF 3 )(L) (L = PPh 3 , PEt 3 , PF 3 , CNMe, CNPh, CNCF 3 , a n d CS (from CS 2 a n d PPh 3 )) used similar methodology. 5 Photolysis of Mn(Cp*)(CO)3 directly in the presence of excess CNCF 3 a f f o r d e d Mn(Cp*)(CNCF 3 ) 3 . 4 F r o m I R evidence for the series Mn(Cp*)(CO) 2 (L) (L = CO, CNMe, CS, a n d CNCF 3 )…”

Low-valent Organorhenium Compounds

“…Thus, hydride reduction of dication (82) generates cationic formyl and methyl (83) complexes (Scheme 18). 195 ' 196 The enantiomers of (83) were resolved as (lS)-3-bromocamphorsulfonate salts and treatment of optically pure (83) with aqueous acid gave methane and the halide complex with retention of configuration at rhenium. Acids with nonnucleophilic counterions such as 1 M HC10 4 or H 2 SO 4 do not react with (83).…”

“…195 ' 196 The enantiomers of (83) were resolved as (lS)-3-bromocamphorsulfonate salts and treatment of optically pure (83) with aqueous acid gave methane and the halide complex with retention of configuration at rhenium. Acids with nonnucleophilic counterions such as 1 M HC10 4 or H 2 SO 4 do not react with (83). The protonation reaction has been proposed to involve dissociation and protonation of a secondary amine ligand followed by loss o f methane and halide attack.…”