Journal article
Metal-metal multiple bonds. 20. Structural, kinetic, and theoretical studies of the reactivity of dimolybdenum .mu.-alkylidenes toward small molecules. Structures of M2(.mu.-CAr2), M2(.mu.-CAr2'), and M2(.mu.-.eta.1,.eta.2-iso-PrNC:CAr2') [M = Cp(or Cp')Mo(CO)2; Ar = p-tolyl, Ar2' = 2,2'-biphenylenyl, and Cp' = C5H4Me]
Journal of the American Chemical Society, Vol.109(12), pp.3603-3616
06/01/1987
DOI: 10.1021/ja00246a017
Abstract
The reactions of the dimolybdenum p-alkylidene complexes M2(p-CAr2) (M = Mo(CO)2Cp or Cp’ (Cp ‘ = C5H4Me); Ar2= phenyl, p-tolyl (2a,b), or 2,2/-biphenyIenyl (2c)) with CO, H2, Ar2CN2, R3P, isonitriles, alkenes, and alkynes are reported. The kinetics of the reaction of M2(p-CPh2) with CO is interpreted in terms of the detachment of one coordinated phenyl group to provide a vacant coordination site prior to attack by CO. The differences in reactivity of 2a,b compared with 2c are explained on the basis of an EHMO analysis of the bonding in these complexes. The structures of 2b, 2c, and the reaction product M2(¼-n1,n,n2-z-PrNC—CAr2) (8), from 2c and i-PrNC, are discussed, as are the dynamical behavior of these molecules in solution. Crystallographic data for 2b-PhMe: a = 18.481 (8) Å, b = 19.095 (5) Å, c = 10.065 (3) Å, a = 90.01 (2)°,² = 105.76 (3)°, 7 = 117.01 (3)°, V = 3014 (2) Å3, Z = 4, pc= 1.55 g/mL, space group = PI, RuR2= 0.057, 0.078 on 6085 reflections with I> 3(7(7). Crystallographic data for 2c: a = 11.716 (5) Å, b = 12.152 (6) Å, c = 17.488 (4) Å, ² = 108.77 (3)°, V = 2358 (2) Å3, Z = 4, pc= 1.76 g/mL, space group P2Jc, RuR2= 0.036, 0.056 on 3381 reflections with 7 > 3 3
Details
- Title: Subtitle
- Metal-metal multiple bonds. 20. Structural, kinetic, and theoretical studies of the reactivity of dimolybdenum .mu.-alkylidenes toward small molecules. Structures of M2(.mu.-CAr2), M2(.mu.-CAr2'), and M2(.mu.-.eta.1,.eta.2-iso-PrNC:CAr2') [M = Cp(or Cp')Mo(CO)2; Ar = p-tolyl, Ar2' = 2,2'-biphenylenyl, and Cp' = C5H4Me]
- Creators
- M. David CurtisL MesserleJohn J D'ErricoHugo E SolisIcela D BarceloW. M Butler
- Resource Type
- Journal article
- Publication Details
- Journal of the American Chemical Society, Vol.109(12), pp.3603-3616
- Publisher
- American Chemical Society
- DOI
- 10.1021/ja00246a017
- ISSN
- 0002-7863
- eISSN
- 1520-5126
- Language
- English
- Date published
- 06/01/1987
- Academic Unit
- Chemistry; Radiology
- Record Identifier
- 9984216599302771
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