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Models for multicenter catalysts. 4. Reactions of binuclear hydrides with alkynes and the structure of (Ir sub 2 (H) sub 2 Cl(CH sub 3 O sub 2 CC double bond C(H)CO sub 2 CH sub 3 ) sub 2 (CO) sub 2 (Ph sub 2 PCH sub 2 PPh sub 2 ) sub 2 )-(BF sub 4 ) sm bullet 3THF, a model hydrogenation intermediate containing mutually adjacent alkenyl and hydrido ligands

Journal Article · · Organometallics; (USA)
DOI:https://doi.org/10.1021/om00119a035· OSTI ID:6429086
;  [1]
  1. Univ. of Alberta, Edmonton (Canada)
The reaction of (Ir{sub 2}(H){sub 2}(CO){sub 2}({mu}-Cl)(DPM){sub 2})(BF{sub 4}) (1) with 2 equiv of dimethyl acetylenedicarboxylate (DMA) in THF or acetone yields (Ir{sub 2}(CH{sub 3}O{sub 2}CC{double bond}C(H)CO{sub 2}CH{sub 3}){sub 2}(CO){sub 2}({mu}-Cl)(DPM){sub 2})(BF{sub 4}). This cationic species is the result of alkyne insertion into both of the Ir-H bonds of compound 1. Further reaction of this species with dihydrogen yields (Ir{sub 2}(H){sub 2}Cl(CH{sub 3}O{sub 2}CC{double bond}C(H)CO{sub 2}CH{sub 3}){sub 2}(CO){sub 2}(DPM){sub 2})(BF{sub 4}) (DPM = Ph{sub 2}PCH{sub 2}PPh{sub 2}), which is a stable complex containing mutually adjacent alkenyl and hydrido ligands. This compound crystallizes in the space group P2{sub 1}/c with a = 18.675 (5) {angstrom}, b = 15.775 (3) {angstrom}, c = 26.371 (4) {angstrom}, {beta} = 96.38 (2){degree}, and Z = 4.
OSTI ID:
6429086
Journal Information:
Organometallics; (USA), Journal Name: Organometallics; (USA) Vol. 9:5; ISSN 0276-7333; ISSN ORGND
Country of Publication:
United States
Language:
English