Stabilizing heterobimetallic complexes containing unsupported Ti-M bonds (M = Fe, Ru, Co): the nature of Ti-M donor-acceptor bonds

Friedrich, S. and Memmler, H. and Gade, L. H. and Li, W.-S. and Scowen, I. J. and McPartlin, M. and Housecroft, C. E. (1996) Stabilizing heterobimetallic complexes containing unsupported Ti-M bonds (M = Fe, Ru, Co): the nature of Ti-M donor-acceptor bonds. Inorganic Chemistry, 35 (9). pp. 2433-2441. ISSN 0020-1669

Full content URL: http://dx.doi.org/10.1021/ic951353f

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Item Type:Article
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Abstract

The stabilization of unsupported Ti-M (M = Fe, Ru, Co) heterodinuclear complexes has been achieved by use of amidotitanium building blocks containing tripodal amido ligands. Salt metathesis of H3CC(CH2NSiMe3)3TiX (1) and C6H5C(CH2NSiMe3)3TiX (2) as well as HCSiMe2N(4-CH3C6H4)3TiX (3) (X = Cl, a; Br, b) with KM(CO)2Cp (M = Fe, Ru) and NaCo(CO)3(PR3) (R = Ph, Tol) gave the corresponding stable heterobimetallic complexes of which H3CC(CH2NSiMe3)3Ti-M(CO) 2Cp (M = Fe, 6; Ru, 7) and HC{SiMe2N(4-CH3C6H4)} 3-Ti-M(CO)2Cp (M = Fe, 12; Ru, 13) have been characterized by X-ray crystallography. 6: monoclinic, P21/n, a = 15.496(3) à , b = 12.983(3) à , c = 29.219(3) à , β= 104.52(2)°, Z = 8, V = 5690.71 à 3, R = 0.070. 7: monoclinic, P21/c, a = 12.977(3) à , b = 12.084(3) à , c = 18.217(3) à , β= 91.33(2)°, Z = 4, V= 2855.91 à 3, R = 0.048. 12: monoclinic, I2/c, a = 24.660(4) à , b = 15.452(3) à , c = 20.631(4) à , β= 103.64(3)°, Z = 8, V = 7639.65 à 3, R = 0.079. 13: monoclinic, I2/c, a = 24.473(3) à , b = 15.417(3) à , c = 20.783(4) à , β= 104.20(2)°, Z = 8, V = 7601.84 à 3, R = 0.066. 1H- and 13C-NMR studies in solution indicate free internal rotation of the molecular fragments around the Ti-M bonds. Fenske - Hall calculations performed on the idealized system HC(CH2NH)3Ti-Fe(CO)2Cp (6x) have revealed a significant degree of �-donor-acceptor interaction between the two metal fragments reinforcing the Ti-Fe �-bond. Due to the availability of energetically low-lying �-acceptor orbitals at the Ti center this partial multiple bonding is more pronounced that in the tin analogue HC(CH2NH)3Sn-Fe(CO)2Cp (15x) in which an N-Sn �*-orbital may act as �-acceptor orbital.

Keywords:Chemistry
Subjects:F Physical Sciences > F100 Chemistry
Divisions:College of Science > School of Chemistry
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ID Code:13094
Deposited On:19 Mar 2014 19:03

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