Synthesis and Reactivity of A Neutral Tungsten(o) Alkyl Complex: Insertion of C0 2 into The W-ch 3 bond of Trans,trans-w(ch 3 )(co)2(no)(pph3)2 and The Structural Characterization of Trans-w(η 2 -02cch 3 )(c0)(n0)(pph 3 ) 2

Mark M. Holl, Gregory L. Hillhouse, Kirsten Folting, John C. Huffman

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Abstract

Reaction of trans,trans-WCl(CO) 2 (NO)(PPh 3 )2 (1) with CH 3 Li or (CH 3 ) 2 Zn affords trans,trans-W-(CH 3 HCO) 2 (NO)(PPh 3 ) 2 (2) in good yields. Treatment of 2 with DC1 gives 1 and CH 3 D quantitatively. Reaction of 2 with carbon monoxide (2 atm, 80 °C) results in a reversible substitution of CO for PPh 3 to give mer-W(CH 3 )(CO) 3 (NO)(PPh 3 ) (3). Carbon dioxide undergoes a 1,2-insertion reaction with 2 to give the monodentate acetate complex trans,trans-W[η 1 -0C(0)CH 3 ](C0) 2 (N0)(PPh 3 ) 2 (4), which reversibly loses CO on heating to yield the bidentate acetate derivative trans-W(η 2 -0 2 CCH 3 )(C0)(N0)(PPh 3 ) 2 (5). Monoclinic prisms of 5 were grown from a dichloromethane/benzene solution and crystallized in space group P2 1 /a with Z = 4, a = 20.864 (5) A, b = 9.729 (2) A, c = 17.504 (4) A, and β = 103.21 (1)°. An X-ray diffraction study at -91 ± 3 °C showed that the acetate ligand is bound in an asymmetric fashion to the tungsten center and that the nitrosyl and carbonyl ligands are not substantially disordered. Salient metrical parameters of the structure include the following: W(l)-0(4) == 2.249 (5) A, W(l)-0(5) = 2.217 (5) A, 0(4)-C(6) = 1.270 (10) A, 0(5)-C(6) = 1.302 (10) A, W(l)-C(8) = 1.914 (8) A, C(8)-0(9) = 1.171 (9) A, W(l)-N(10) = 1.836 (7) A, N(10)-O(ll) = 1.203 (9) A, and W(l)-N(10)-O(ll) = 178.3 (6)°. The least-squares refinement converged to R(F) = 0.036 and R w (F) = 0.036 for 3518 unique data with F > 3σ(F).

Original languageEnglish
Pages (from-to)1522-1527
Number of pages6
JournalOrganometallics
Volume6
Issue number7
DOIs
Publication statusPublished - 1 Jul 1987
Externally publishedYes

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