Novel hemilabile (phosphinoalkyl)arene ligands: Mechanistic investigation of an unusual intramolecular, arene-arene exchange reaction

Elizabeth T. Singewald; Xiaobo Shi; Chad A. Mirkin; Susan J. Schofer; Charlotte L. Stern

doi:10.1021/om960114c

Novel hemilabile (phosphinoalkyl)arene ligands: Mechanistic investigation of an unusual intramolecular, arene-arene exchange reaction

Elizabeth T. Singewald, Xiaobo Shi, Chad A. Mirkin^*, Susan J. Schofer, Charlotte L. Stern

^*Corresponding author for this work

Chemistry

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Abstract

The novel, hemilabile (phosphinoalkyl)arene ligands ArX(CH₂)₂PPh₂ (1a, Ar = C₆H₅, X = O; 1b, Ar = C₆H₅, X = CH₂; 1c, Ar = FC₆H₄, X = CH₂) were synthesized and complexed to Rh(I) to form the bis(phosphine), η⁶-arene piano stool complexes [(η⁶:η¹-ArX(CH₂)₂PPh ₂)Rh(η¹-ArX(CH₂)₂PPh ₂)]BF₄ (2a-c). Complexes 2a-c were fully characterized in solution, and complex 2a was characterized by single-crystal X-ray diffraction methods. Two of these complexes, 2a,c, undergo an unusual, degenerate η⁶-arene, free arene exchange reaction which was studied by 2-D NMR EXSY experiments. A mechanism for the exchange reaction of 2a which involves the formation of a square planar, cis-phosphine, cis-ether Rh(I) complex, [Rh(η²-PhO(CH₂)₂PPh₂) ₂]BF₄ (13), is proposed.

Original language	English (US)
Pages (from-to)	3062-3069
Number of pages	8
Journal	Organometallics
Volume	15
Issue number	13
DOIs	https://doi.org/10.1021/om960114c
State	Published - Jun 25 1996

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Novel hemilabile (phosphinoalkyl)arene ligands: Mechanistic investigation of an unusual intramolecular, arene-arene exchange reaction",

abstract = "The novel, hemilabile (phosphinoalkyl)arene ligands ArX(CH2)2PPh2 (1a, Ar = C6H5, X = O; 1b, Ar = C6H5, X = CH2; 1c, Ar = FC6H4, X = CH2) were synthesized and complexed to Rh(I) to form the bis(phosphine), η6-arene piano stool complexes [(η6:η1-ArX(CH2)2PPh 2)Rh(η1-ArX(CH2)2PPh 2)]BF4 (2a-c). Complexes 2a-c were fully characterized in solution, and complex 2a was characterized by single-crystal X-ray diffraction methods. Two of these complexes, 2a,c, undergo an unusual, degenerate η6-arene, free arene exchange reaction which was studied by 2-D NMR EXSY experiments. A mechanism for the exchange reaction of 2a which involves the formation of a square planar, cis-phosphine, cis-ether Rh(I) complex, [Rh(η2-PhO(CH2)2PPh2) 2]BF4 (13), is proposed.",

author = "Singewald, {Elizabeth T.} and Xiaobo Shi and Mirkin, {Chad A.} and Schofer, {Susan J.} and Stern, {Charlotte L.}",

year = "1996",

month = jun,

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doi = "10.1021/om960114c",

language = "English (US)",

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AU - Singewald, Elizabeth T.

AU - Shi, Xiaobo

AU - Mirkin, Chad A.

AU - Schofer, Susan J.

AU - Stern, Charlotte L.

PY - 1996/6/25

Y1 - 1996/6/25

N2 - The novel, hemilabile (phosphinoalkyl)arene ligands ArX(CH2)2PPh2 (1a, Ar = C6H5, X = O; 1b, Ar = C6H5, X = CH2; 1c, Ar = FC6H4, X = CH2) were synthesized and complexed to Rh(I) to form the bis(phosphine), η6-arene piano stool complexes [(η6:η1-ArX(CH2)2PPh 2)Rh(η1-ArX(CH2)2PPh 2)]BF4 (2a-c). Complexes 2a-c were fully characterized in solution, and complex 2a was characterized by single-crystal X-ray diffraction methods. Two of these complexes, 2a,c, undergo an unusual, degenerate η6-arene, free arene exchange reaction which was studied by 2-D NMR EXSY experiments. A mechanism for the exchange reaction of 2a which involves the formation of a square planar, cis-phosphine, cis-ether Rh(I) complex, [Rh(η2-PhO(CH2)2PPh2) 2]BF4 (13), is proposed.

AB - The novel, hemilabile (phosphinoalkyl)arene ligands ArX(CH2)2PPh2 (1a, Ar = C6H5, X = O; 1b, Ar = C6H5, X = CH2; 1c, Ar = FC6H4, X = CH2) were synthesized and complexed to Rh(I) to form the bis(phosphine), η6-arene piano stool complexes [(η6:η1-ArX(CH2)2PPh 2)Rh(η1-ArX(CH2)2PPh 2)]BF4 (2a-c). Complexes 2a-c were fully characterized in solution, and complex 2a was characterized by single-crystal X-ray diffraction methods. Two of these complexes, 2a,c, undergo an unusual, degenerate η6-arene, free arene exchange reaction which was studied by 2-D NMR EXSY experiments. A mechanism for the exchange reaction of 2a which involves the formation of a square planar, cis-phosphine, cis-ether Rh(I) complex, [Rh(η2-PhO(CH2)2PPh2) 2]BF4 (13), is proposed.

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Novel hemilabile (phosphinoalkyl)arene ligands: Mechanistic investigation of an unusual intramolecular, arene-arene exchange reaction

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