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Dinuclear cyclopentadienyl carbonyl and alkyne complexes of niobium(II) and tantalum(II). Structures of ((C sub 5 H sub 4 Me)Nb(. mu. -Cl)(CO) sub 2 ) sub 2 , ((C sub 5 H sub 4 Me)Nb(. mu. -Cl)(ArC triple bond CAr)) sub 2 , and ((C sub 5 Me sub 5 )Ta(. mu. -Cl)(CO) sub 2 ) sub 2

Journal Article · · Organometallics; (United States)
DOI:https://doi.org/10.1021/om00047a041· OSTI ID:6106825
; ;  [1]; ;  [2]
  1. Univ. of Michigan, Ann Arbor (United States)
  2. Univ. of Delaware, Newark (United States)
+ Show Author Affiliations
The M(III) complexes (M = Nb, Ta) (({eta}{sup 5}-C{sub 5}H{sub 4}Me)NbCl({mu}-Cl)(CO){sub 2}){sub 2}, ({eta}{sup 5}-C{sub 5}H{sub 4}Me)NbCl{sub 2}(ArCCAr), and ({eta}{sup 5}-C{sub 5}Me{sub 5})TaCl{sub 2}(CO){sub 2}(THF) were reduced with Na/Hg to give diamagnetic M(II) dinuclear complexes with M-M bonds: (({eta}{sup 5}-C{sub 5}H{sub 4}Me)Nb({mu}-Cl)(CO){sub 2}){sub 2} (1), (({eta}{sup 5}-C{sub 5}H{sub 4}Me)Nb({mu}-Cl)(ArCCAr)){sub 2} (2a), and (({eta}{sup 5}-C{sub 5}Me{sub 5})Ta({mu}-Cl)(CO){sub 2}){sub 2} (3), respectively (Ar = 4-methylphenyl). The structures of 1, 2a, and 3 were determined by single-crystal X-ray diffractometry. Crystal data for 1: space group P{bar 1}, Z = 2, a = 10.279 (3) {angstrom}, b = 11.247 (3) {angstrom}, c = 8.587 (2) {angstrom}, V = 904.6 (4) {angstrom}{sup 3}, R = 0.031, R{sub w} = 0.034 based on 2667 reflections with I > 3{sigma}(I). Crystal data for 2a: space group P{bar 1}, Z = 1, a = 9.623 (3) {angstrom}, b = 9.781 (3) {angstrom}, C = 12.245 (4) {angstrom}, V = 933.5 (6) {angstrom}{sup 3}, R = 0.032, R{sub w} = 0.031 based on 2710 reflections with I > 3{sigma}(I). Crystal data for 3: space group P2{sub 1}/n, Z = 4, a = 8.660 (2) {angstrom}, b = 14.790 (3) {angstrom}, c = 21.009 (7) {angstrom}, {beta} = 98.81 (2){degree}, V = 2659.7 (16) {angstrom}{sup 3}, R = 0.039, R{sub w} = 0.041 based on 3,816 reflections with I > 3{sigma}(I). The structures of carbonyl complexes 1 and 3 and alkyne complex 2a are considerably different; 1 and 3 have folded M{sub 2}Cl{sub 2} cores, whereas 2a has a centrosymmetric structure with a planar M{sub 2}Cl{sub 2} core.
OSTI ID:
6106825
Journal Information:
Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 10:1; ISSN 0276-7333; ISSN ORGND
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKENES
ALKYNES
ALLOYS
BOND ANGLE
BOND LENGTHS
CHEMICAL PREPARATION
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
CYCLOALKENES
CYCLOPENTADIENE
DIENES
DIFFRACTION
DIMENSIONS
HYDROCARBONS
LENGTH
MASS SPECTRA
MERCURY ALLOYS
MOLECULAR STRUCTURE
NIOBIUM COMPLEXES
NMR SPECTRA
ORGANIC COMPOUNDS
POLYENES
SCATTERING
SPECTRA
SYNTHESIS
TANTALUM COMPLEXES
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION