Synthesis and structure determination of two unusual dirhodium complexes having thiolato and carbonyl bridging ligands

Herbert Schumann; Stanislaw Jurgis; Moris Eisen; Jochanan Blum

doi:10.1016/S0020-1693(00)80856-7

Synthesis and structure determination of two unusual dirhodium complexes having thiolato and carbonyl bridging ligands

Herbert Schumann^*, Stanislaw Jurgis, Moris Eisen, Jochanan Blum

^*Corresponding author for this work

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

8 Scopus citations

Abstract

Two unusual carbonyl bridged dirhodium complexes [(CH₃)₂PC₆H₅](CO)Rh(μ-CO)(μ-SC₆H₁₁)₂-RhCl₂[(CH₃)₂PC₆H₅](7) and [(CH₃)₂PC₆H₅]₂ClRh-(μ-CO)(μ-Cl)(μ-SC₆H₁₁)RhCl[(CH₃)₂PC₆H₅] (8) were obtained from the reaction of [Rh(CO)₂]₂(μ-Cl)₂ (1) with (CH₃)₂PC₆H₅ (4) and (CH₃)₃SiSC₆H₁₁ (5). Their geometric structures as well as the structure of trans-RhCl(CO)[(CH₃)₂PC₆H₅]₂ (6) were determined by X-ray diffraction analysis, and qualitative molecular orbital pictures were obtained from extended Hückel molecular orbital (EHMO) calculations. Both dirhodium complexes can be described in terms of the combination of one square pyramid and one octahedron. Complex 6 is square planar and belongs to space group P1 with a = 10.277(2), b = 15.881(3), c = 6.025(1) Å; α = 96.60(4), β = 93.65(5), γ = 83.81(5)°; Z = 2; R = 0.043 and R_w = 0.069 for 2702 reflections with I≥ 3σ_I. Compound 7 belongs to space group P2₁/n with a = 11.976(3), b = 22.721(4), c = 14.153(3) Å; β = 97.03(5)°; Z = 4; R = 0.066 and R_w = 0.087 for 3204 reflections with I≥3σ_I. The two rhodium atoms are connected by two cyclohexylthiolato bridges and by one carbonyl bridge. The Rh(1)-Rh(2) distance is 2.848 Å, yet EHMO calculations indicate no direct interactions between the two metal atoms. Complex 8 belongs to space group P2₁/c with a = 15.832(4), b = 11.080, c = 21.407(5) Å; β = 108.66(5)°; Z = 4; R = 0.047 and R_w = 0.067 for 3699 reflections with I≥ 2σ_I. Chlorine, carbonyl and cyclohexylthiolato groups serve as bridging ligands. The Rh(1)-Rh(2) distance is of the same order of magnitude as in 7 (2.873 Å), yet the calculations reveal some metal-metal interactions that involve the d(xy) and d(z²) orbitals of both rhodium atoms. The existence of Rh(1)-Rh(2) interactions is also confirmed by the temperature dependent ESR spectrum.

Original language	English
Pages (from-to)	191-201
Number of pages	11
Journal	Inorganica Chimica Acta
Volume	172
Issue number	2
DOIs	https://doi.org/10.1016/S0020-1693(00)80856-7
State	Published - 15 Jun 1990
Externally published	Yes

Access to Document

10.1016/S0020-1693(00)80856-7

Cite this

@article{87d272879ff043778f40fceed5f66e96,

title = "Synthesis and structure determination of two unusual dirhodium complexes having thiolato and carbonyl bridging ligands",

abstract = "Two unusual carbonyl bridged dirhodium complexes [(CH3)2PC6H5](CO)Rh(μ-CO)(μ-SC6H11)2-RhCl2[(CH3)2PC6H5](7) and [(CH3)2PC6H5]2ClRh-(μ-CO)(μ-Cl)(μ-SC6H11)RhCl[(CH3)2PC6H5] (8) were obtained from the reaction of [Rh(CO)2]2(μ-Cl)2 (1) with (CH3)2PC6H5 (4) and (CH3)3SiSC6H11 (5). Their geometric structures as well as the structure of trans-RhCl(CO)[(CH3)2PC6H5]2 (6) were determined by X-ray diffraction analysis, and qualitative molecular orbital pictures were obtained from extended H{\"u}ckel molecular orbital (EHMO) calculations. Both dirhodium complexes can be described in terms of the combination of one square pyramid and one octahedron. Complex 6 is square planar and belongs to space group P1 with a = 10.277(2), b = 15.881(3), c = 6.025(1) {\AA}; α = 96.60(4), β = 93.65(5), γ = 83.81(5)°; Z = 2; R = 0.043 and Rw = 0.069 for 2702 reflections with I≥ 3σI. Compound 7 belongs to space group P21/n with a = 11.976(3), b = 22.721(4), c = 14.153(3) {\AA}; β = 97.03(5)°; Z = 4; R = 0.066 and Rw = 0.087 for 3204 reflections with I≥3σI. The two rhodium atoms are connected by two cyclohexylthiolato bridges and by one carbonyl bridge. The Rh(1)-Rh(2) distance is 2.848 {\AA}, yet EHMO calculations indicate no direct interactions between the two metal atoms. Complex 8 belongs to space group P21/c with a = 15.832(4), b = 11.080, c = 21.407(5) {\AA}; β = 108.66(5)°; Z = 4; R = 0.047 and Rw = 0.067 for 3699 reflections with I≥ 2σI. Chlorine, carbonyl and cyclohexylthiolato groups serve as bridging ligands. The Rh(1)-Rh(2) distance is of the same order of magnitude as in 7 (2.873 {\AA}), yet the calculations reveal some metal-metal interactions that involve the d(xy) and d(z2) orbitals of both rhodium atoms. The existence of Rh(1)-Rh(2) interactions is also confirmed by the temperature dependent ESR spectrum.",

author = "Herbert Schumann and Stanislaw Jurgis and Moris Eisen and Jochanan Blum",

note = "Funding Information: We wish to thank Dr Shmuel Cohen for his help in the X-ray analyses, Professor A. Y. Meyer for his help in the EHMO calculations and for most useful suggestions, the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie for financial",

year = "1990",

month = jun,

day = "15",

doi = "10.1016/S0020-1693(00)80856-7",

language = "英语",

volume = "172",

pages = "191--201",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

publisher = "Elsevier BV",

number = "2",

}

TY - JOUR

T1 - Synthesis and structure determination of two unusual dirhodium complexes having thiolato and carbonyl bridging ligands

AU - Schumann, Herbert

AU - Jurgis, Stanislaw

AU - Eisen, Moris

AU - Blum, Jochanan

N1 - Funding Information: We wish to thank Dr Shmuel Cohen for his help in the X-ray analyses, Professor A. Y. Meyer for his help in the EHMO calculations and for most useful suggestions, the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie for financial

PY - 1990/6/15

Y1 - 1990/6/15

N2 - Two unusual carbonyl bridged dirhodium complexes [(CH3)2PC6H5](CO)Rh(μ-CO)(μ-SC6H11)2-RhCl2[(CH3)2PC6H5](7) and [(CH3)2PC6H5]2ClRh-(μ-CO)(μ-Cl)(μ-SC6H11)RhCl[(CH3)2PC6H5] (8) were obtained from the reaction of [Rh(CO)2]2(μ-Cl)2 (1) with (CH3)2PC6H5 (4) and (CH3)3SiSC6H11 (5). Their geometric structures as well as the structure of trans-RhCl(CO)[(CH3)2PC6H5]2 (6) were determined by X-ray diffraction analysis, and qualitative molecular orbital pictures were obtained from extended Hückel molecular orbital (EHMO) calculations. Both dirhodium complexes can be described in terms of the combination of one square pyramid and one octahedron. Complex 6 is square planar and belongs to space group P1 with a = 10.277(2), b = 15.881(3), c = 6.025(1) Å; α = 96.60(4), β = 93.65(5), γ = 83.81(5)°; Z = 2; R = 0.043 and Rw = 0.069 for 2702 reflections with I≥ 3σI. Compound 7 belongs to space group P21/n with a = 11.976(3), b = 22.721(4), c = 14.153(3) Å; β = 97.03(5)°; Z = 4; R = 0.066 and Rw = 0.087 for 3204 reflections with I≥3σI. The two rhodium atoms are connected by two cyclohexylthiolato bridges and by one carbonyl bridge. The Rh(1)-Rh(2) distance is 2.848 Å, yet EHMO calculations indicate no direct interactions between the two metal atoms. Complex 8 belongs to space group P21/c with a = 15.832(4), b = 11.080, c = 21.407(5) Å; β = 108.66(5)°; Z = 4; R = 0.047 and Rw = 0.067 for 3699 reflections with I≥ 2σI. Chlorine, carbonyl and cyclohexylthiolato groups serve as bridging ligands. The Rh(1)-Rh(2) distance is of the same order of magnitude as in 7 (2.873 Å), yet the calculations reveal some metal-metal interactions that involve the d(xy) and d(z2) orbitals of both rhodium atoms. The existence of Rh(1)-Rh(2) interactions is also confirmed by the temperature dependent ESR spectrum.

AB - Two unusual carbonyl bridged dirhodium complexes [(CH3)2PC6H5](CO)Rh(μ-CO)(μ-SC6H11)2-RhCl2[(CH3)2PC6H5](7) and [(CH3)2PC6H5]2ClRh-(μ-CO)(μ-Cl)(μ-SC6H11)RhCl[(CH3)2PC6H5] (8) were obtained from the reaction of [Rh(CO)2]2(μ-Cl)2 (1) with (CH3)2PC6H5 (4) and (CH3)3SiSC6H11 (5). Their geometric structures as well as the structure of trans-RhCl(CO)[(CH3)2PC6H5]2 (6) were determined by X-ray diffraction analysis, and qualitative molecular orbital pictures were obtained from extended Hückel molecular orbital (EHMO) calculations. Both dirhodium complexes can be described in terms of the combination of one square pyramid and one octahedron. Complex 6 is square planar and belongs to space group P1 with a = 10.277(2), b = 15.881(3), c = 6.025(1) Å; α = 96.60(4), β = 93.65(5), γ = 83.81(5)°; Z = 2; R = 0.043 and Rw = 0.069 for 2702 reflections with I≥ 3σI. Compound 7 belongs to space group P21/n with a = 11.976(3), b = 22.721(4), c = 14.153(3) Å; β = 97.03(5)°; Z = 4; R = 0.066 and Rw = 0.087 for 3204 reflections with I≥3σI. The two rhodium atoms are connected by two cyclohexylthiolato bridges and by one carbonyl bridge. The Rh(1)-Rh(2) distance is 2.848 Å, yet EHMO calculations indicate no direct interactions between the two metal atoms. Complex 8 belongs to space group P21/c with a = 15.832(4), b = 11.080, c = 21.407(5) Å; β = 108.66(5)°; Z = 4; R = 0.047 and Rw = 0.067 for 3699 reflections with I≥ 2σI. Chlorine, carbonyl and cyclohexylthiolato groups serve as bridging ligands. The Rh(1)-Rh(2) distance is of the same order of magnitude as in 7 (2.873 Å), yet the calculations reveal some metal-metal interactions that involve the d(xy) and d(z2) orbitals of both rhodium atoms. The existence of Rh(1)-Rh(2) interactions is also confirmed by the temperature dependent ESR spectrum.

UR - http://www.scopus.com/inward/record.url?scp=0011660010&partnerID=8YFLogxK

U2 - 10.1016/S0020-1693(00)80856-7

DO - 10.1016/S0020-1693(00)80856-7

M3 - 文章

AN - SCOPUS:0011660010

SN - 0020-1693

VL - 172

SP - 191

EP - 201

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

IS - 2

ER -

Synthesis and structure determination of two unusual dirhodium complexes having thiolato and carbonyl bridging ligands

Abstract

Access to Document

Other files and links

Fingerprint

Cite this