10.1021/om051084t

Arsaalkenes R-As=C(NMe2)(2) [R = PhC(O), 4-EtC6H4C(O), 2,4,6-Me3C6H2C(O), t-BuC(O), Me3Si]: Versatile reagents in the chemistry of heterocumulenes

Abstract

Weber L, Bayer P, Braun T, Stammler H-G, Neumann B. Arsaalkenes R-As=C(NMe2)(2) [R = PhC(O), 4-EtC6H4C(O), 2,4,6-Me3C6H2C(O), t-BuC(O), Me3Si]: Versatile reagents in the chemistry of heterocumulenes. Organometallics. 2006;25(7):1786-1794.Reaction of [Cp(CO)(2)M=P=C(SiMe3)(2.)] (where M = Mo (3a), W (3b)] with 2 equiv of the arsaalkene PhC(O)As=C(NMe2)(2) afforded the metalloarsaalkenes Cp(CO)(2)M-As=C(Ph)-O-P-O-C(Ph)=As-C(SiMe3)(2) [where M= Mo (6a), W (6b)]. Small amounts of [{eta(3):eta(3)-(Me3Si)(2)CPAs-AsPC(SiMe3)(2)}- {Mo(CO)(2)Cp}(2)] (7) were formed as a minor product. Similarly, 3b and 2 equiv of 4-EtC6H4C(O)As= C(NMe2)(2) gave rise to the formation of [Cp(CO)(2)W-As=C(4-EtC6H4)-O-P-O-C(4-EtC6H4)=As- C(SiMe3)(2)] (8). However, treatment of 3a and 3b with an excess of tBuC(O)As=C(NMe2)(2) yielded cocrystals of the eta(3)-2-phospha-1,3-diarsaallyl complexes [Cp(CO)(2)M{eta(3)-tBuC(O)AsPAsC(O)tBu}] [where M = Mo (13a), W (13b)] and the eta(3)-1,2,3-triarsaallyl complexes [Cp(CO)(2)M{eta(3-)tBuC(O)AsAsAsC-(O)tBu}] [where M = Mo (14a), W (14b)] in varying ratios. Reaction of 3a with Me3SiAs=C(NMe2)(2) afforded the dinuclear 1,2-diphosphapropene complex [{eta(2):eta(2)-(Me3Si)(2)C=P-P(H)-C(H)(SiMe3)(2)}{Mo-(CO)(2)Cp}(2)] (15). The novel compounds 6a,b, 8, 13a,b, 14a,b, and 15 were characterized by means of spectroscopy (IR and H-1, C-13{H-1}, P-31 NMR). Moreover the molecular structures of 7, 8, 13a, 14a, 13b, 14b, and 15 were determined by X-ray diffraction analyses

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oai:pub.uni-bielefeld.de:1599848Last time updated on 9/5/2013

This paper was published in Publications at Bielefeld University.

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