Synthesis of molybdenum-rhodium and molybdenum-iridium compounds linked by a heterodifunctional ligand and formation of molybdenum-iridium dihydrides by reaction with molecular hydrogen

Charles P. Casey; R Morris Bullock; Francois Nief

Synthesis of molybdenum-rhodium and molybdenum-iridium compounds linked by a heterodifunctional ligand and formation of molybdenum-iridium dihydrides by reaction with molecular hydrogen

Charles P. Casey, R Morris Bullock, Francois Nief

Pacific Northwest National Laboratory

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

72 Citations (Scopus)

Abstract

A series of Rh-Mo and Ir-Mo compounds linked by a heterodifunctional ligand have been prepared. Li⁺[η⁵-C₅H₄P(C₆H ₄-p-CH₃)₂]Mo(CO)₃ ^- (1) reacted with the chlorine-bridged rhodium dimer {[(C₆H₄-p-CH₃)₂PCH₂] ₂RhCl}₂ (2) to give [(C₆H₄-p-CH₃)₂PCH₂] ₂RhMo(CO)₃[η⁵-C₅H ₄P(C₆H₄-p-CH₃)₂] (3). Reaction of 1 with [(CO)₂RhCl]₂ gave (CO)₂RhMo(CO)₃[η⁵-C₅H ₄P(C₆H₄-p-CH₃)₂] (4). P(C₆H₄-p-CH₃)₃ or P(CH₃)₃ reacted with 4 to give phosphine substitution products trans-P(C₆H₄-p-CH₃) ₃(CO)RhMo(CO)₃[η⁵-C₅H ₄P(C₆H₄-p-CH₃)₂] (5) and trans-P(CH₃)₃(CO)RhMo(CO)₃-[η ⁵-C₅H₄P(C₆H₄-p-CH ₃)₂] (6), respectively. None of these rhodium-molybdenum compounds reacted with H₂ to form observable metal hydrides. Reaction of 1 with (CO)₂IrCl(H₂NC₆H₄-P-CH₃) provided iridium-molybdenum compound 8, (CO)₂ IrMo(CO)₃[η⁵-C₅H₄P(C ₆H₄-p-CH₃)₂]. Reaction of 8 with P(CH₃)₃ or P(C₆H₅)₃ gave phosphine substitution products trans-P(CH₃)₃(CO)IrMo(CO)₃[η ⁵-C₅H₄P(C₆H₄-p-CH ₃)₂] (9) and trans-P(C₆H₅)₃(CO)IrMo(CO) ₃[η⁵-C₅H₄P(C₆H ₄-p-CH₃)₂] (10), respectively. Compounds 8, 9, and 10 reacted readily with H₂ at room temperature and atmospheric pressure to give Mo-IrH₂ compounds 11, 12, and 13.

Original language	English
Pages (from-to)	7574-7580
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	105
Issue number	26
Publication status	Published - 1983

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Chemistry(all)

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Synthesis of molybdenum-rhodium and molybdenum-iridium compounds linked by a heterodifunctional ligand and formation of molybdenum-iridium dihydrides by reaction with molecular hydrogen. / Casey, Charles P.; Bullock, R Morris; Nief, Francois.

In: Journal of the American Chemical Society, Vol. 105, No. 26, 1983, p. 7574-7580.

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

@article{d184a627ca4f4966a0f128446618aec1,

title = "Synthesis of molybdenum-rhodium and molybdenum-iridium compounds linked by a heterodifunctional ligand and formation of molybdenum-iridium dihydrides by reaction with molecular hydrogen",

abstract = "A series of Rh-Mo and Ir-Mo compounds linked by a heterodifunctional ligand have been prepared. Li+[η5-C5H4P(C6H 4-p-CH3)2]Mo(CO)3 - (1) reacted with the chlorine-bridged rhodium dimer {[(C6H4-p-CH3)2PCH2] 2RhCl}2 (2) to give [(C6H4-p-CH3)2PCH2] 2RhMo(CO)3[η5-C5H 4P(C6H4-p-CH3)2] (3). Reaction of 1 with [(CO)2RhCl]2 gave (CO)2RhMo(CO)3[η5-C5H 4P(C6H4-p-CH3)2] (4). P(C6H4-p-CH3)3 or P(CH3)3 reacted with 4 to give phosphine substitution products trans-P(C6H4-p-CH3) 3(CO)RhMo(CO)3[η5-C5H 4P(C6H4-p-CH3)2] (5) and trans-P(CH3)3(CO)RhMo(CO)3-[η 5-C5H4P(C6H4-p-CH 3)2] (6), respectively. None of these rhodium-molybdenum compounds reacted with H2 to form observable metal hydrides. Reaction of 1 with (CO)2IrCl(H2NC6H4-P-CH3) provided iridium-molybdenum compound 8, (CO)2 IrMo(CO)3[η5-C5H4P(C 6H4-p-CH3)2]. Reaction of 8 with P(CH3)3 or P(C6H5)3 gave phosphine substitution products trans-P(CH3)3(CO)IrMo(CO)3[η 5-C5H4P(C6H4-p-CH 3)2] (9) and trans-P(C6H5)3(CO)IrMo(CO) 3[η5-C5H4P(C6H 4-p-CH3)2] (10), respectively. Compounds 8, 9, and 10 reacted readily with H2 at room temperature and atmospheric pressure to give Mo-IrH2 compounds 11, 12, and 13.",

author = "Casey, {Charles P.} and Bullock, {R Morris} and Francois Nief",

year = "1983",

language = "English",

volume = "105",

pages = "7574--7580",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "26",

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TY - JOUR

T1 - Synthesis of molybdenum-rhodium and molybdenum-iridium compounds linked by a heterodifunctional ligand and formation of molybdenum-iridium dihydrides by reaction with molecular hydrogen

AU - Casey, Charles P.

AU - Bullock, R Morris

AU - Nief, Francois

PY - 1983

Y1 - 1983

N2 - A series of Rh-Mo and Ir-Mo compounds linked by a heterodifunctional ligand have been prepared. Li+[η5-C5H4P(C6H 4-p-CH3)2]Mo(CO)3 - (1) reacted with the chlorine-bridged rhodium dimer {[(C6H4-p-CH3)2PCH2] 2RhCl}2 (2) to give [(C6H4-p-CH3)2PCH2] 2RhMo(CO)3[η5-C5H 4P(C6H4-p-CH3)2] (3). Reaction of 1 with [(CO)2RhCl]2 gave (CO)2RhMo(CO)3[η5-C5H 4P(C6H4-p-CH3)2] (4). P(C6H4-p-CH3)3 or P(CH3)3 reacted with 4 to give phosphine substitution products trans-P(C6H4-p-CH3) 3(CO)RhMo(CO)3[η5-C5H 4P(C6H4-p-CH3)2] (5) and trans-P(CH3)3(CO)RhMo(CO)3-[η 5-C5H4P(C6H4-p-CH 3)2] (6), respectively. None of these rhodium-molybdenum compounds reacted with H2 to form observable metal hydrides. Reaction of 1 with (CO)2IrCl(H2NC6H4-P-CH3) provided iridium-molybdenum compound 8, (CO)2 IrMo(CO)3[η5-C5H4P(C 6H4-p-CH3)2]. Reaction of 8 with P(CH3)3 or P(C6H5)3 gave phosphine substitution products trans-P(CH3)3(CO)IrMo(CO)3[η 5-C5H4P(C6H4-p-CH 3)2] (9) and trans-P(C6H5)3(CO)IrMo(CO) 3[η5-C5H4P(C6H 4-p-CH3)2] (10), respectively. Compounds 8, 9, and 10 reacted readily with H2 at room temperature and atmospheric pressure to give Mo-IrH2 compounds 11, 12, and 13.

AB - A series of Rh-Mo and Ir-Mo compounds linked by a heterodifunctional ligand have been prepared. Li+[η5-C5H4P(C6H 4-p-CH3)2]Mo(CO)3 - (1) reacted with the chlorine-bridged rhodium dimer {[(C6H4-p-CH3)2PCH2] 2RhCl}2 (2) to give [(C6H4-p-CH3)2PCH2] 2RhMo(CO)3[η5-C5H 4P(C6H4-p-CH3)2] (3). Reaction of 1 with [(CO)2RhCl]2 gave (CO)2RhMo(CO)3[η5-C5H 4P(C6H4-p-CH3)2] (4). P(C6H4-p-CH3)3 or P(CH3)3 reacted with 4 to give phosphine substitution products trans-P(C6H4-p-CH3) 3(CO)RhMo(CO)3[η5-C5H 4P(C6H4-p-CH3)2] (5) and trans-P(CH3)3(CO)RhMo(CO)3-[η 5-C5H4P(C6H4-p-CH 3)2] (6), respectively. None of these rhodium-molybdenum compounds reacted with H2 to form observable metal hydrides. Reaction of 1 with (CO)2IrCl(H2NC6H4-P-CH3) provided iridium-molybdenum compound 8, (CO)2 IrMo(CO)3[η5-C5H4P(C 6H4-p-CH3)2]. Reaction of 8 with P(CH3)3 or P(C6H5)3 gave phosphine substitution products trans-P(CH3)3(CO)IrMo(CO)3[η 5-C5H4P(C6H4-p-CH 3)2] (9) and trans-P(C6H5)3(CO)IrMo(CO) 3[η5-C5H4P(C6H 4-p-CH3)2] (10), respectively. Compounds 8, 9, and 10 reacted readily with H2 at room temperature and atmospheric pressure to give Mo-IrH2 compounds 11, 12, and 13.

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VL - 105

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EP - 7580

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