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Title: 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

Abstract

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.

Authors:
;  [1]
  1. Univ. of Alberta, Edmonton (Canada)
Publication Date:
OSTI Identifier:
6429086
Resource Type:
Journal Article
Journal Name:
Organometallics; (USA)
Additional Journal Information:
Journal Volume: 9:5; Journal ID: ISSN 0276-7333
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALKYNES; CHEMICAL REACTIONS; CATALYSTS; HYDRIDES; CRYSTAL STRUCTURE; DATA ANALYSIS; EXPERIMENTAL DATA; HYDROGENATION; IRIDIUM; MEASURING INSTRUMENTS; MEASURING METHODS; DATA; ELEMENTS; HYDROCARBONS; HYDROGEN COMPOUNDS; INFORMATION; METALS; NUMERICAL DATA; ORGANIC COMPOUNDS; PLATINUM METALS; TRANSITION ELEMENTS; 400201* - Chemical & Physicochemical Properties

Citation Formats

Vaartstra, B A, and Cowie, M. 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. United States: N. p., 1990. Web. doi:10.1021/om00119a035.
Vaartstra, B A, & Cowie, M. 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. United States. https://doi.org/10.1021/om00119a035
Vaartstra, B A, and Cowie, M. 1990. "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". United States. https://doi.org/10.1021/om00119a035.
@article{osti_6429086,
title = {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},
author = {Vaartstra, B A and Cowie, M},
abstractNote = {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.},
doi = {10.1021/om00119a035},
url = {https://www.osti.gov/biblio/6429086}, journal = {Organometallics; (USA)},
issn = {0276-7333},
number = ,
volume = 9:5,
place = {United States},
year = {Tue May 01 00:00:00 EDT 1990},
month = {Tue May 01 00:00:00 EDT 1990}
}