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

doi:10.1021/om00081a023

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

Chemistry and Biochemistry

Research output: Contribution to journal › Article › peer-review

21 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, M_r = 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, D_calcd = 1.593 g cm^-3, Z = 2, λ(Mo k_α) = 0.71069 Å (graphite monochromator), μ(Mo K_α) = 15.43 cm^-1, final R = 0.047, R_w = 0.055 from 2804 observed reflections (3617 measured). Crystal data for 4: C₂₀H₃₆As₄Cl₂CrO₄, M_r = 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, D_calacd = 1.723 g cm^-3, Z = 8, λ(Mo K_α) = 0.71069 Å (graphite monochromator), μ(Mo K_α) = 53.2 cm^-1, final R = 0.054, R_w = 0.073 from 4100 observed reflections (11533 measured).

Original language	English
Pages (from-to)	469-475
Number of pages	7
Journal	Organometallics
Volume	3
Issue number	3
DOIs	https://doi.org/10.1021/om00081a023
State	Published - Jan 1984

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@article{281d2dabcb644bb39be4a3027f8d3157,

title = "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",

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) {\AA}). 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) {\AA}, b = 9.483 (3) {\AA}, c = 11.778 (5) {\AA}, α = 87.86 (4)°, β = 70.67 (3)°, Γ = 77.77 (3)°, U = 967.3 (5) {\AA}3, Dcalcd = 1.593 g cm-3, Z = 2, λ(Mo kα) = 0.71069 {\AA} (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) {\AA}, b = 35.190 (5) {\AA}, c = 15.303 (3) {\AA}, β = 97.815 (15)°, U = 5884.5 (3) {\AA}3, Dcalacd = 1.723 g cm-3, Z = 8, λ(Mo Kα) = 0.71069 {\AA} (graphite monochromator), μ(Mo Kα) = 53.2 cm-1, final R = 0.054, Rw = 0.073 from 4100 observed reflections (11533 measured).",

author = "Jones, {Richard A.} and Whittlesey, {Bruce R.}",

year = "1984",

month = jan,

doi = "10.1021/om00081a023",

language = "English",

volume = "3",

pages = "469--475",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "3",

}

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. / Jones, Richard A.; Whittlesey, Bruce R.
In: Organometallics, Vol. 3, No. 3, 01.1984, p. 469-475.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - 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

AU - Jones, Richard A.

AU - Whittlesey, Bruce R.

PY - 1984/1

Y1 - 1984/1

N2 - 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).

AB - 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).

UR - http://www.scopus.com/inward/record.url?scp=0000200018&partnerID=8YFLogxK

U2 - 10.1021/om00081a023

DO - 10.1021/om00081a023

M3 - Article

AN - SCOPUS:0000200018

SN - 0276-7333

VL - 3

SP - 469

EP - 475

JO - Organometallics

JF - Organometallics

IS - 3