84 - J . C HEM. S OC., C HEM. COMMUN., 1989 1411 Synthesis...

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J. CHEM. SOC., CHEM. COMMUN., 1989 141 1 Synthesis of Tetranuclear and Pentanuclear Vanadium-Oxide-Carboxylate Aggregates Dwight D. Heinrich, Kirsten Folting, William E. Streib, John C. Huffman, and George Christou" Department of Chemistry and the Molecular Structure Center, Indiana University, Bloomington, IN 47405, U.S.A. Treatment of V0Cl42- with tca- (tca- = thiophene-2-carboxylate) under aerobic conditions leads to formation of [V509Cl(t~a)4]2-, whereas if AgN03 is also present, the product is [V40s(N03)(t~a)4]2-; the two anions have been isolated as NR4+ salts and their unusual structures elucidated by crystallographic methods. As part of our continuing interest in the structural and (PhCH2NEt3)2[VOC14] with two equivalents of Na(tca) (tca- reactivity chemistry of vanadium with oxygen and/or sulphur = thiophene-2-carboxylate) in MeCN under aerobic condi- ligands,l+ we have been exploring the chemistry of this metal tions led to formation of a deep green solution stable to with functionalized thiophene groups. In one such experi- prolonged exposure to air. A precipitate of NaCl was removed ment, treatment of the hydrolytically-sensitive salt by filtration and the filtrate concentrated by
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1412 J. CHEM. SOC., CHEM. COMMUN., 1989 \ / O(9) \ /- r W 34 4) Figure 1. Top and side views of the anion of complex (1). Selected distances (A) and angles (") are: V(l) . - . V(2) 3.485(2), V(2) - . V(3) 3.472(2), V(3) * * - V(4) 3.483(2), V(4) * . V(l) 3.484(2), V(5) * * * V(l) 2.893(2), V(5) * * * V(2) 2.906(2), V(5) - * * V(3) 2.908(2), V(5) * . * V(4) 2.898(2), C1(6)-V(1) 2.959(3), C1(6)-V(2) 2.974(3), C1(6)-V(3) 3.067(3), C1(6)-V(4) 2.880(3), V(1)-0(11) 1.588(6), V(2)-0( 12) 1.589(6), V(3)-O( 13) 1.588(6), V( 4)-O( 14) 1.599( 6), V(5)-0( 15) 1.597(6), V(5)-0(7) 1.874(6), V(5)-O( 8) 1.880(6), V(5)-0(9) 1.894(6), V(5)-O( 10) 1.885(6), O(7)-V( 1) 1.953(6), 0(7)-V(2) 1.961(6), 0(8)-V(2) 1.963(6), 0(8)-V(3) 1.948(6), O(9)- V(3) 1.954(6), 0(9)-V(4) 1.970(6), 0(10)-V(4) 1.967(6), O(10)-V(l) 1.985 (6), V( 1,2,3,4)-0 ( 16,18,24,26,32,34,40,42) 2.005 (6)-2.033 (6) ; V( l)-C1(6)-V(2) 71.94(6) ; V( 1)-C1(6)-V(4) 73.24( 6); V(2)-C1(6)- V( 3) 70.14( 6) V( 3)-C1(6)-V(4) 7 1.61 (6). to produce dark green crystals. These were collected by filtration, washed with tetrahydrofuran (THF) and ether and dried in air. The product was identified by analysis? and T The analytical data for complex (1) (C, H, N, S, C1, V) and (2) (C, H, N, S, V) were satisfactory. crystallography$ as (PhCH2NEt3)2[V509C1(tca)4].MeCN (1) in 7540% yield. The structure of the anion is shown in Figure 1, and consists of a V5 square pyramid with a p3-02- bridging each triangular face and a p-tca- bridging each basal edge. Each V possesses a terminal, multiply-bonded oxide. The basal V atoms V(1-4) are additionally ligated to C1(6),
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84 - J . C HEM. S OC., C HEM. COMMUN., 1989 1411 Synthesis...

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