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

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Abstract

A series of Rh-Mo and Ir-Mo compounds linked by a heterodifunctional ligand have been prepared. Li+5-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)35-C5H 4P(C6H4-p-CH3)2] (3). Reaction of 1 with [(CO)2RhCl]2 gave (CO)2RhMo(CO)35-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)35-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)35-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)35-C5H4P(C6H4-p-CH 3)2] (9) and trans-P(C6H5)3(CO)IrMo(CO) 35-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 languageEnglish
Pages (from-to)7574-7580
Number of pages7
JournalJournal of the American Chemical Society
Volume105
Issue number26
Publication statusPublished - 1983

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phosphine
Iridium compounds
Molybdenum compounds
Iridium
Rhodium
Molybdenum
Hydrogen
Substitution reactions
Ligands
Chlorine
Hydrides
Dimers
Atmospheric pressure
Atmospheric Pressure
Metals
Temperature
8-1 compound

ASJC Scopus subject areas

  • Chemistry(all)

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@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",

}

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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M3 - Article

VL - 105

SP - 7574

EP - 7580

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 26

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