Solid-State structure and solution reactivity of [(Ph3P)4Ru(H)2] and related Ru(II) complexes used in catalysis: A reinvestigation

Hamidreza Samouei; Fedor M. Miloserdov; Eduardo C. Escudero-Adán; Vladimir V. Grushin

doi:10.1021/om5010572

Solid-State structure and solution reactivity of [(Ph₃P)₄Ru(H)₂] and related Ru(II) complexes used in catalysis: A reinvestigation

Hamidreza Samouei, Fedor M. Miloserdov, Eduardo C. Escudero-Adán, Vladimir V. Grushin^*

^*Corresponding author for this work

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

24 Citations (Scopus)

Abstract

X-ray analysis of [(Ph₃P)₄Ru(H)₂] (1) prepared by a literature procedure [ Young, R.; Wilkinson, G. Inorg. Synth. 1990, 28, 337 ] shows that 1 is cocrystallized with PPh₃, explaining the previously reported observations of free phosphine in solutions of 1. Lattice PPh₃-free forms of 1 have also been obtained, structurally characterized, and found to generate small quantities of uncoordinated PPh₃ and another species (A) in solution. Against previous beliefs, however, A is not [(Ph₃P)₃Ru(H)₂] (2), but [(Ph₃P)₃Ru(H₂)(H)₂] (3) that forms in the reaction of 1 with adventitious water. This reaction apparently occurs via PPh₃ loss from 1 to give 2, followed by H₂O coordination, Ru(H)(OH₂)/Ru(H₂)(OH) rearrangement, H₂ loss, and dimerization to give [(Ph₃P)₄Ru₂(H)₂(μ-OH)₂] (4). The H₂ thus produced is trapped with 2 to give 3. Complexes 3·0.5C₆H₆, 3·2THF, 4·2H₂O, [(Ph₃P)₃Ru(N₂)(H)₂] (5), and [(Ph₃P)₂(H)Ru(μ-H)₃Ru(PPh₃)₃]·0.5THF (6·0.5THF) have been structurally characterized for the first time. Also for the first time, a single-crystal X-ray diffraction study of the long-known [(Ph₃P)₄RuCl₂] (7) has been performed to finally demonstrate that 7 is, in fact, [(Ph₃P)₃RuCl₂]·PPh₃, precisely as proposed by Hoffman and Caulton as early as 1975 [ Hoffman, P.R.; Caulton, K.G. J. Am. Chem. Soc. 1975, 97, 4221 ].

Original language	English
Pages (from-to)	7279-7283
Number of pages	5
Journal	Organometallics
Volume	33
Issue number	24
DOIs	https://doi.org/10.1021/om5010572
Publication status	Published - 22 Dec 2014
Externally published	Yes

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@article{ae7181a9359e41a098e09b5a6a14dcbd,

title = "Solid-State structure and solution reactivity of [(Ph3P)4Ru(H)2] and related Ru(II) complexes used in catalysis: A reinvestigation",

abstract = "X-ray analysis of [(Ph3P)4Ru(H)2] (1) prepared by a literature procedure [ Young, R.; Wilkinson, G. Inorg. Synth. 1990, 28, 337 ] shows that 1 is cocrystallized with PPh3, explaining the previously reported observations of free phosphine in solutions of 1. Lattice PPh3-free forms of 1 have also been obtained, structurally characterized, and found to generate small quantities of uncoordinated PPh3 and another species (A) in solution. Against previous beliefs, however, A is not [(Ph3P)3Ru(H)2] (2), but [(Ph3P)3Ru(H2)(H)2] (3) that forms in the reaction of 1 with adventitious water. This reaction apparently occurs via PPh3 loss from 1 to give 2, followed by H2O coordination, Ru(H)(OH2)/Ru(H2)(OH) rearrangement, H2 loss, and dimerization to give [(Ph3P)4Ru2(H)2(μ-OH)2] (4). The H2 thus produced is trapped with 2 to give 3. Complexes 3·0.5C6H6, 3·2THF, 4·2H2O, [(Ph3P)3Ru(N2)(H)2] (5), and [(Ph3P)2(H)Ru(μ-H)3Ru(PPh3)3]·0.5THF (6·0.5THF) have been structurally characterized for the first time. Also for the first time, a single-crystal X-ray diffraction study of the long-known [(Ph3P)4RuCl2] (7) has been performed to finally demonstrate that 7 is, in fact, [(Ph3P)3RuCl2]·PPh3, precisely as proposed by Hoffman and Caulton as early as 1975 [ Hoffman, P.R.; Caulton, K.G. J. Am. Chem. Soc. 1975, 97, 4221 ].",

author = "Hamidreza Samouei and Miloserdov, \{Fedor M.\} and Escudero-Ad{\'a}n, \{Eduardo C.\} and Grushin, \{Vladimir V.\}",

year = "2014",

month = dec,

day = "22",

doi = "10.1021/om5010572",

language = "English",

volume = "33",

pages = "7279--7283",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society (ACS)",

number = "24",

}

TY - JOUR

T1 - Solid-State structure and solution reactivity of [(Ph3P)4Ru(H)2] and related Ru(II) complexes used in catalysis

T2 - A reinvestigation

AU - Samouei, Hamidreza

AU - Miloserdov, Fedor M.

AU - Escudero-Adán, Eduardo C.

AU - Grushin, Vladimir V.

PY - 2014/12/22

Y1 - 2014/12/22

N2 - X-ray analysis of [(Ph3P)4Ru(H)2] (1) prepared by a literature procedure [ Young, R.; Wilkinson, G. Inorg. Synth. 1990, 28, 337 ] shows that 1 is cocrystallized with PPh3, explaining the previously reported observations of free phosphine in solutions of 1. Lattice PPh3-free forms of 1 have also been obtained, structurally characterized, and found to generate small quantities of uncoordinated PPh3 and another species (A) in solution. Against previous beliefs, however, A is not [(Ph3P)3Ru(H)2] (2), but [(Ph3P)3Ru(H2)(H)2] (3) that forms in the reaction of 1 with adventitious water. This reaction apparently occurs via PPh3 loss from 1 to give 2, followed by H2O coordination, Ru(H)(OH2)/Ru(H2)(OH) rearrangement, H2 loss, and dimerization to give [(Ph3P)4Ru2(H)2(μ-OH)2] (4). The H2 thus produced is trapped with 2 to give 3. Complexes 3·0.5C6H6, 3·2THF, 4·2H2O, [(Ph3P)3Ru(N2)(H)2] (5), and [(Ph3P)2(H)Ru(μ-H)3Ru(PPh3)3]·0.5THF (6·0.5THF) have been structurally characterized for the first time. Also for the first time, a single-crystal X-ray diffraction study of the long-known [(Ph3P)4RuCl2] (7) has been performed to finally demonstrate that 7 is, in fact, [(Ph3P)3RuCl2]·PPh3, precisely as proposed by Hoffman and Caulton as early as 1975 [ Hoffman, P.R.; Caulton, K.G. J. Am. Chem. Soc. 1975, 97, 4221 ].

AB - X-ray analysis of [(Ph3P)4Ru(H)2] (1) prepared by a literature procedure [ Young, R.; Wilkinson, G. Inorg. Synth. 1990, 28, 337 ] shows that 1 is cocrystallized with PPh3, explaining the previously reported observations of free phosphine in solutions of 1. Lattice PPh3-free forms of 1 have also been obtained, structurally characterized, and found to generate small quantities of uncoordinated PPh3 and another species (A) in solution. Against previous beliefs, however, A is not [(Ph3P)3Ru(H)2] (2), but [(Ph3P)3Ru(H2)(H)2] (3) that forms in the reaction of 1 with adventitious water. This reaction apparently occurs via PPh3 loss from 1 to give 2, followed by H2O coordination, Ru(H)(OH2)/Ru(H2)(OH) rearrangement, H2 loss, and dimerization to give [(Ph3P)4Ru2(H)2(μ-OH)2] (4). The H2 thus produced is trapped with 2 to give 3. Complexes 3·0.5C6H6, 3·2THF, 4·2H2O, [(Ph3P)3Ru(N2)(H)2] (5), and [(Ph3P)2(H)Ru(μ-H)3Ru(PPh3)3]·0.5THF (6·0.5THF) have been structurally characterized for the first time. Also for the first time, a single-crystal X-ray diffraction study of the long-known [(Ph3P)4RuCl2] (7) has been performed to finally demonstrate that 7 is, in fact, [(Ph3P)3RuCl2]·PPh3, precisely as proposed by Hoffman and Caulton as early as 1975 [ Hoffman, P.R.; Caulton, K.G. J. Am. Chem. Soc. 1975, 97, 4221 ].

U2 - 10.1021/om5010572

DO - 10.1021/om5010572

M3 - Article

AN - SCOPUS:84919724690

SN - 0276-7333

VL - 33

SP - 7279

EP - 7283

JO - Organometallics

JF - Organometallics

IS - 24

ER -

Solid-State structure and solution reactivity of [(Ph3P)4Ru(H)2] and related Ru(II) complexes used in catalysis: A reinvestigation

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Solid-State structure and solution reactivity of [(Ph₃P)₄Ru(H)₂] and related Ru(II) complexes used in catalysis: A reinvestigation