Masters Theses

Date of Award

5-1992

Degree Type

Thesis

Degree Name

Master of Science

Major

Chemistry

Major Professor

Craig E. Barnes

Committee Members

Clifton Woods, Edward Clark

Abstract

The synthesis of two novel trinuclear organometallic complexes based upon the series prepared by Barnes et al. (Organometallics, 1990, 9, 1021) is presented. Reaction of (η5-C5Me5Co)2 (μ-CO) (μ-NO) (1) with (η5-C5H5Co) (C2H4)2 yields (η5-C5Me5Co)2 (μ3 - CO)(μ3 - NO) (η5-C5H5Co)(4), a 47 electron paramagnetic trinuclear cluster. Attempted dinuclear exchange reactions between 4 and (η5-C5Me5Rh)2(μ-CO)2 (2) yield no novel trinuclear clusters containing the nitrosyl moiety. Likewise, reactions of 1 with members of the series synthesized by Barnes et al. do not yield 4 as a product. The X-ray crystal data for 4 are as follows: monoclinic, P21/n, a = 8.692(10)Å, b= 17.482(2)Å, c = 16.278(3)Å, β= 103.550(10)°, Z = 4, R(F) = 2.92%. Reaction of (η5-C5Me5M)x(μ3-CO)2(η5-C5H5Co)3-x (M= Co, Rh; x = 1, 2 ) with N2CHCH3 yields a 48 electron diazoalkane adduct, where the diazoalkane assumes a monohapto-, triply- bridging coordination mode, as verified by X-ray crystal analysis of 3 (M = Co, x = 1) . A similar reaction of (η5-C5Me5Co) (μ3-CO)2(η5-C5H5Co)2 with N2CH2 yields a diazoalkane adduct, while reaction of (η5-C5Me5Rh) (μ3-CO)2(η5-C5H5Co)2 with N2CH2 yields a trinuclear carbene complex which undergoes isomerization in solution. The X-ray crystal data for 3 are as follows: monoclinic, P21/c, a= 8.846(2)Å, b= 9.701(2)Å, c= 28.587(5)Å, β= 97.825(14)°, Z- 4, R(F)= 3.31%.

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