Metal-metal multiple bonds. 20. Structural, kinetic, and theoretical studies of the reactivity of dimolybdenum. mu. -alkylidenes toward small molecules. Structures of M/sub 2/(. mu. -CAr/sub 2/), M/sub 2/(. mu. -CAr/sub 2/'), and M/sub 2/(. mu. -eta/sup 1/,eta/sup 2/-i-PrNC = CAr/sub 2/') (M = Cp(or Cp')Mo(CO)/sub 2/, Ar = p-Tolyl, Ar/sub 2/' = 2,2'-biphenylenyl, and Cp' = C/sub 5/H/sub 4/Me)

Journal Article · Wed Jun 10 04:00:00 EDT 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00246a017· OSTI ID:6036753

Curtis, M D; Messerle, L; D'Errico, J J; Solis, H E; Barcelo, I D; Butler, W M

The reactions of the dimolybdenum ..mu..-alkylidene complexes M/sub 2/(..mu..-CAr/sub 2/) (M = Mo(CO)/sub 2/Cp or Cp' (Cp' = C/sub 5/H/sub 4/Me); Ar/sub 2/ = phenyl, p-tolyl (2a,b), or 2,2'-biphenylenyl (2c)) with CO, H/sub 2/, Ar/sub 2/CN/sub 2/, R/sub 3/P, isonitriles, alkenes, and alkynes are reported. The kinetics of the reaction of M/sub 2/(..mu..-CPh/sub 2/) 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 M/sub 2/(..mu..-eta/sup 1/,eta/sup 2/-i-PrNC double bond CAr/sub 2/) (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), b = 19.095 (5) A, c = 10.065 (3) A, ..cap alpha.. = 90.01 (2)/sup 0/, ..beta.. = 105.76 (3)/sup 0/, ..gamma.. = 117.01 (3)/sup 0/, V = 3014 (2) A/sup 3/, Z = 4, rho/sub c/ = 1.55 g/mL, space group = P1, R/sub 1/, R/sub 2/ = 0.057, 0.078 on 6085 reflections with I > 3sigma(I). Crystallographic data for 2c: a = 11.716 (5) A, b = 12.152 (6) A, c = 17.488 (4) A, ..beta.. = 108.77 (3)/sup 0/, V = 2358 (2) A/sup 3/, Z = 4, rho/sub c/ = 1.76 g/mL, space group P2/sub 1//c, R/sub 1/, R/sub 2/ = 0.036, 0.056 on 3381 reflections with I > 3sigma (I). Crystallographic data for 8: a = 8.486 (3) A, b = 20.16 (1) A, c = 16.75 (7) A, ..beta.. = 92.31 (7)/sup 0/, V = 2863 (4) A/sup 3/, Z = 4, rho/sub c/ = 1.71 g/mL, space group = P2/sub 1//c, R/sub 1/, R/sub 2/ = 0.045, 0.039 on 2297 reflections with I > 3sigma(I).

• Research Organization: Univ. of Michigan, Ann Arbor
• OSTI ID: 6036753
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:12; ISSN JACSA
• Country of Publication: United States
• Language: English

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