Chiral organometallic triangles with Rh-Rh bonds. 1. Compounds prepared from racemic cis-Rh2(C6H4PPh2) 2(OAc)2

F. Albert Cotton; Carlos A. Murillo; Xiaoping Wang; Rongmin Yu

doi:10.1021/ic0492183

Chiral organometallic triangles with Rh-Rh bonds. 1. Compounds prepared from racemic cis-Rh₂(C₆H₄PPh₂) ₂(OAc)₂

F. Albert Cotton, Carlos A. Murillo, Xiaoping Wang, Rongmin Yu

Texas A&M University

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

59 Scopus citations

Abstract

Reaction of racemic cis-Rh₂(C₆H₄PPh ₂)₂(OAc)₂(HOAc)₂ with excess Me ₃OBF₄ in CH₃CN results in the formation of racemic cis-[Rh₂(C₆H₄PPh₂) ₂(CH₃CN)₆](BF₄)₂· 0.5H₂O (1-0.5H₂O), an ionic dirhodium complex which has two cisoid nonlabile orthometalated phosphine bridging anions and six labile CH₃CN ligands in equatorial and axial positions. Reactions of 1 with tetraethylammonium salts of the linear dicarboxylates, oxalate, terephthalate, and 4,4′-biphenyl-dicarboxylate, in organic solvents, produced racemic crystals of the triangular compounds [Rh₂(C₆H ₄PPh₂)₂]₃(C₂O ₄)₃-(py)₆·6MeOH·H₂O (2·6MeOH·H₂O), [Rh₂(C₆H ₄PPh₂)₂]₃(O₂CC ₆H₄CO₂)₃(DMF)₆·6. 5DMF·0.5H₂O(3·6.5DMF·0.5H₂O), and [Rh₂(C₆H₄PPh₂)₂] ₃(O₂CC₆H₄C₆H ₄CO₂)₃(py)₆·4.5CH ₃OH·0.75H₂O (4-4.5CH₃OH·0. 75H₂O), respectively. All compounds are electrochemically active. The relative chiralities of the dirhodium units in each triangle have been established using a combination of data from X-ray crystallography and ³¹P NMR spectroscopy.

Original language	English
Pages (from-to)	8394-8403
Number of pages	10
Journal	Inorganic Chemistry
Volume	43
Issue number	26
DOIs	https://doi.org/10.1021/ic0492183
State	Published - Dec 27 2004
Externally published	Yes

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@article{479acfacff2b4e948539ca5ac91485ca,

title = "Chiral organometallic triangles with Rh-Rh bonds. 1. Compounds prepared from racemic cis-Rh2(C6H4PPh2) 2(OAc)2",

abstract = "Reaction of racemic cis-Rh2(C6H4PPh 2)2(OAc)2(HOAc)2 with excess Me 3OBF4 in CH3CN results in the formation of racemic cis-[Rh2(C6H4PPh2) 2(CH3CN)6](BF4)2· 0.5H2O (1-0.5H2O), an ionic dirhodium complex which has two cisoid nonlabile orthometalated phosphine bridging anions and six labile CH3CN ligands in equatorial and axial positions. Reactions of 1 with tetraethylammonium salts of the linear dicarboxylates, oxalate, terephthalate, and 4,4′-biphenyl-dicarboxylate, in organic solvents, produced racemic crystals of the triangular compounds [Rh2(C6H 4PPh2)2]3(C2O 4)3-(py)6·6MeOH·H2O (2·6MeOH·H2O), [Rh2(C6H 4PPh2)2]3(O2CC 6H4CO2)3(DMF)6·6. 5DMF·0.5H2O(3·6.5DMF·0.5H2O), and [Rh2(C6H4PPh2)2] 3(O2CC6H4C6H 4CO2)3(py)6·4.5CH 3OH·0.75H2O (4-4.5CH3OH·0. 75H2O), respectively. All compounds are electrochemically active. The relative chiralities of the dirhodium units in each triangle have been established using a combination of data from X-ray crystallography and 31P NMR spectroscopy.",

author = "Cotton, {F. Albert} and Murillo, {Carlos A.} and Xiaoping Wang and Rongmin Yu",

year = "2004",

month = dec,

day = "27",

doi = "10.1021/ic0492183",

language = "English",

volume = "43",

pages = "8394--8403",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "26",

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T1 - Chiral organometallic triangles with Rh-Rh bonds. 1. Compounds prepared from racemic cis-Rh2(C6H4PPh2) 2(OAc)2

AU - Cotton, F. Albert

AU - Murillo, Carlos A.

AU - Wang, Xiaoping

AU - Yu, Rongmin

PY - 2004/12/27

Y1 - 2004/12/27

N2 - Reaction of racemic cis-Rh2(C6H4PPh 2)2(OAc)2(HOAc)2 with excess Me 3OBF4 in CH3CN results in the formation of racemic cis-[Rh2(C6H4PPh2) 2(CH3CN)6](BF4)2· 0.5H2O (1-0.5H2O), an ionic dirhodium complex which has two cisoid nonlabile orthometalated phosphine bridging anions and six labile CH3CN ligands in equatorial and axial positions. Reactions of 1 with tetraethylammonium salts of the linear dicarboxylates, oxalate, terephthalate, and 4,4′-biphenyl-dicarboxylate, in organic solvents, produced racemic crystals of the triangular compounds [Rh2(C6H 4PPh2)2]3(C2O 4)3-(py)6·6MeOH·H2O (2·6MeOH·H2O), [Rh2(C6H 4PPh2)2]3(O2CC 6H4CO2)3(DMF)6·6. 5DMF·0.5H2O(3·6.5DMF·0.5H2O), and [Rh2(C6H4PPh2)2] 3(O2CC6H4C6H 4CO2)3(py)6·4.5CH 3OH·0.75H2O (4-4.5CH3OH·0. 75H2O), respectively. All compounds are electrochemically active. The relative chiralities of the dirhodium units in each triangle have been established using a combination of data from X-ray crystallography and 31P NMR spectroscopy.

AB - Reaction of racemic cis-Rh2(C6H4PPh 2)2(OAc)2(HOAc)2 with excess Me 3OBF4 in CH3CN results in the formation of racemic cis-[Rh2(C6H4PPh2) 2(CH3CN)6](BF4)2· 0.5H2O (1-0.5H2O), an ionic dirhodium complex which has two cisoid nonlabile orthometalated phosphine bridging anions and six labile CH3CN ligands in equatorial and axial positions. Reactions of 1 with tetraethylammonium salts of the linear dicarboxylates, oxalate, terephthalate, and 4,4′-biphenyl-dicarboxylate, in organic solvents, produced racemic crystals of the triangular compounds [Rh2(C6H 4PPh2)2]3(C2O 4)3-(py)6·6MeOH·H2O (2·6MeOH·H2O), [Rh2(C6H 4PPh2)2]3(O2CC 6H4CO2)3(DMF)6·6. 5DMF·0.5H2O(3·6.5DMF·0.5H2O), and [Rh2(C6H4PPh2)2] 3(O2CC6H4C6H 4CO2)3(py)6·4.5CH 3OH·0.75H2O (4-4.5CH3OH·0. 75H2O), respectively. All compounds are electrochemically active. The relative chiralities of the dirhodium units in each triangle have been established using a combination of data from X-ray crystallography and 31P NMR spectroscopy.

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U2 - 10.1021/ic0492183

DO - 10.1021/ic0492183

M3 - Article

AN - SCOPUS:11144338877

SN - 0020-1669

VL - 43

SP - 8394

EP - 8403

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 26

ER -

Chiral organometallic triangles with Rh-Rh bonds. 1. Compounds prepared from racemic cis-Rh₂(C₆H₄PPh₂) ₂(OAc)₂

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