Metal control of the reaction site in reactions of [{(η5-C5H3)2(SiMe2) 2}M2(CO)4(μ-H)]+ (M = Fe, Ru, Os) with nucleophilic amines

Maxim V. Ovchinnikov; Xiaoping Wang; Arthur J. Schultz; Ilia A. Guzei; Robert J. Angelici

doi:10.1021/om020167w

Metal control of the reaction site in reactions of [{(η⁵-C₅H₃)₂(SiMe₂) ₂}M₂(CO)₄(μ-H)]⁺ (M = Fe, Ru, Os) with nucleophilic amines

Maxim V. Ovchinnikov, Xiaoping Wang, Arthur J. Schultz, Ilia A. Guzei, Robert J. Angelici

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

25 Scopus citations

Abstract

Complexes [{(η⁵-C₅H₃)₂(SiMe₂) ₂}M₂(CO)₄(μH)]⁺BF₄ ^- (M = Fe, Ru, Os; 1a-cH^-BF₄^-), which feature a protonated metal-metal bond, were synthesized. While the Fe and Os complexes react with nucleophilic amines (ammonia, MeNH₂, Me₂NH, Et₃N, morpholine) to give the deprotonated complexes {(η⁵-C₅H₃)₂(SiMe₂) ₂}M₂(CO)₄, the Ru complex reacts with amines by undergoing attack at a CO ligand. These differences in reactivity can be understood by considering the CO ligands in the Ru complex to be more electrophilic than those in the analogous Fe and Os complexes, as indicated by the v(CO) values. Molecular structures of 1a-cH⁺BF₄^-, as determined by X-ray diffraction studies, and [{(η⁵C₅H₃)₂(SiMe₂) ₂}Ru₂(CO)₄(μ-H)]⁺OTf^- (1bD⁺TfO^-), aOTfs determined by a neutron diffraction study, show that the bridging hydride ligand is sterically concealed and therefore slow to undergo deprotonation upon reaction with bases.

Original language	English
Pages (from-to)	3292-3296
Number of pages	5
Journal	Organometallics
Volume	21
Issue number	15
DOIs	https://doi.org/10.1021/om020167w
State	Published - Jul 22 2002
Externally published	Yes

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@article{9183f0e70ec346a89b94cc81dcd55635,

title = "Metal control of the reaction site in reactions of [{(η5-C5H3)2(SiMe2) 2}M2(CO)4(μ-H)]+ (M = Fe, Ru, Os) with nucleophilic amines",

abstract = "Complexes [{(η5-C5H3)2(SiMe2) 2}M2(CO)4(μH)]+BF4 - (M = Fe, Ru, Os; 1a-cH-BF4-), which feature a protonated metal-metal bond, were synthesized. While the Fe and Os complexes react with nucleophilic amines (ammonia, MeNH2, Me2NH, Et3N, morpholine) to give the deprotonated complexes {(η5-C5H3)2(SiMe2) 2}M2(CO)4, the Ru complex reacts with amines by undergoing attack at a CO ligand. These differences in reactivity can be understood by considering the CO ligands in the Ru complex to be more electrophilic than those in the analogous Fe and Os complexes, as indicated by the v(CO) values. Molecular structures of 1a-cH+BF4-, as determined by X-ray diffraction studies, and [{(η5C5H3)2(SiMe2) 2}Ru2(CO)4(μ-H)]+OTf- (1bD+TfO-), aOTfs determined by a neutron diffraction study, show that the bridging hydride ligand is sterically concealed and therefore slow to undergo deprotonation upon reaction with bases.",

author = "Ovchinnikov, {Maxim V.} and Xiaoping Wang and Schultz, {Arthur J.} and Guzei, {Ilia A.} and Angelici, {Robert J.}",

year = "2002",

month = jul,

day = "22",

doi = "10.1021/om020167w",

language = "English",

volume = "21",

pages = "3292--3296",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "15",

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TY - JOUR

T1 - Metal control of the reaction site in reactions of [{(η5-C5H3)2(SiMe2) 2}M2(CO)4(μ-H)]+ (M = Fe, Ru, Os) with nucleophilic amines

AU - Ovchinnikov, Maxim V.

AU - Wang, Xiaoping

AU - Schultz, Arthur J.

AU - Guzei, Ilia A.

AU - Angelici, Robert J.

PY - 2002/7/22

Y1 - 2002/7/22

N2 - Complexes [{(η5-C5H3)2(SiMe2) 2}M2(CO)4(μH)]+BF4 - (M = Fe, Ru, Os; 1a-cH-BF4-), which feature a protonated metal-metal bond, were synthesized. While the Fe and Os complexes react with nucleophilic amines (ammonia, MeNH2, Me2NH, Et3N, morpholine) to give the deprotonated complexes {(η5-C5H3)2(SiMe2) 2}M2(CO)4, the Ru complex reacts with amines by undergoing attack at a CO ligand. These differences in reactivity can be understood by considering the CO ligands in the Ru complex to be more electrophilic than those in the analogous Fe and Os complexes, as indicated by the v(CO) values. Molecular structures of 1a-cH+BF4-, as determined by X-ray diffraction studies, and [{(η5C5H3)2(SiMe2) 2}Ru2(CO)4(μ-H)]+OTf- (1bD+TfO-), aOTfs determined by a neutron diffraction study, show that the bridging hydride ligand is sterically concealed and therefore slow to undergo deprotonation upon reaction with bases.

AB - Complexes [{(η5-C5H3)2(SiMe2) 2}M2(CO)4(μH)]+BF4 - (M = Fe, Ru, Os; 1a-cH-BF4-), which feature a protonated metal-metal bond, were synthesized. While the Fe and Os complexes react with nucleophilic amines (ammonia, MeNH2, Me2NH, Et3N, morpholine) to give the deprotonated complexes {(η5-C5H3)2(SiMe2) 2}M2(CO)4, the Ru complex reacts with amines by undergoing attack at a CO ligand. These differences in reactivity can be understood by considering the CO ligands in the Ru complex to be more electrophilic than those in the analogous Fe and Os complexes, as indicated by the v(CO) values. Molecular structures of 1a-cH+BF4-, as determined by X-ray diffraction studies, and [{(η5C5H3)2(SiMe2) 2}Ru2(CO)4(μ-H)]+OTf- (1bD+TfO-), aOTfs determined by a neutron diffraction study, show that the bridging hydride ligand is sterically concealed and therefore slow to undergo deprotonation upon reaction with bases.

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U2 - 10.1021/om020167w

DO - 10.1021/om020167w

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SN - 0276-7333

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Metal control of the reaction site in reactions of [{(η⁵-C₅H₃)₂(SiMe₂) ₂}M₂(CO)₄(μ-H)]⁺ (M = Fe, Ru, Os) with nucleophilic amines

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