Formation of an Arsinidene Complex of Chromium via As-C Bond Cleavage. Further Reaction To Form a CrAs4 Heterometallocycle. Synthesis and X-ray Structures of [Cr(CO)5]2(μ-t-BuAs) and (CO)4CrAs-f-BuCI(f-BuAs)2As-f-BuCI

Richard A. Jones, Bruce R. Whittlesey

Research output: Contribution to journalArticle

20 Scopus citations

Abstract

Reaction of Na2Cr2(CO)10 with t-Bu2AsCl in THF yields blue-green crystalline [Cr(CO)5]2(μ-t-BuAs) (3) in ca. 60% yield. The X-ray crystal structure of 3 shows an arsinidene (t-BuAs) unit bridging two Cr(CO)5 units with no Cr-Cr bond (Cr-Cr = 4.315 (2) Å). The reaction mixture containing 3, in the presence of PPN+Cl-, gives a mononuclear Cr(0) complex containing a CrAs4 heterometallocycle; (CO)4CrAs-t-BuCl(As-t-Bu)2As-t-BuCl (4) in ca. 12% yield. Crystal data for 3: C14H9O10AsCr2, Mr = 516.06, triclinic, P1, a = 9.397 (3) Å, b = 9.483 (3) Å, c = 11.778 (5) Å, α = 87.86 (4)°, β = 70.67 (3)°, Γ = 77.77 (3)°, U = 967.3 (5) Å3, Dcalcd = 1.593 g cm-3, Z = 2, λ(Mo kα) = 0.71069 Å (graphite monochromator), μ(Mo Kα) = 15.43 cm-1, final R = 0.047, Rw = 0.055 from 2804 observed reflections (3617 measured). Crystal data for 4: C20H36As4Cl2CrO4, Mr = 763.10, monoclinic, P21/n, a = 11.0295 (18) Å, b = 35.190 (5) Å, c = 15.303 (3) Å, β = 97.815 (15)°, U = 5884.5 (3) Å3, Dcalacd = 1.723 g cm-3, Z = 8, λ(Mo Kα) = 0.71069 Å (graphite monochromator), μ(Mo Kα) = 53.2 cm-1, final R = 0.054, Rw = 0.073 from 4100 observed reflections (11533 measured).

Original languageEnglish
Pages (from-to)469-475
Number of pages7
JournalOrganometallics
Volume3
Issue number3
DOIs
StatePublished - Jan 1984

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