Silicon-silicon interaction in bis(silylene)iron, disilanyliron, and bis(silyl)iron complexes

Keiji Ueno; Hiromi Tobita; Hiroshi Ogino

doi:10.1016/0022-328X(92)80099-J

Silicon-silicon interaction in bis(silylene)iron, disilanyliron, and bis(silyl)iron complexes

Keiji Ueno, Hiromi Tobita, Hiroshi Ogino

SCI - Chemistry

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

19 Citations (Scopus)

Abstract

²⁹Si NMR coupling constants in a disilanyliron complex CpFe(CO)₂SiMe₂SiMe(O^tBu)₂ (1: CP = η⁵C₅H₅), a bis(silylene)iron complex Cp(OC)Fe{SiMe₂ ⋯ O(^tBu) ⋯ SiMeO^tBu)} (2), and a cis-bis(silyl)iron complex (OC)₄Fe{SiMe₂CH₂CH₂SiMePh} (3) were measured by the INEPT-INADE-QUATE technique. The coupling constant for 2 (28.6 Hz) is much smaller than that for 1 (128 Hz) with a direct Si-Si bond, but larger than that for 3 (2.7 Hz) where there is no direct Si-Si bond. Model calculations using the extended Hückel method indicate that there is no direct bond between the two silicon atoms in the bis(silylene)iron complex Cp(OC)Fe{SiH₂ ⋯ O(H) ⋯ SiH₂}. This means that the coupling in 2 can be described as the sum of the two geminal couplings, ²J(SiFeSi) and ²J(SiOSi).

Original language	English
Pages (from-to)	93-104
Number of pages	12
Journal	Journal of Organometallic Chemistry
Volume	430
Issue number	1
DOIs	https://doi.org/10.1016/0022-328X(92)80099-J
Publication status	Published - 1992 Jun 2

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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@article{a89c1041763c4513ae077368e27e01f0,

title = "Silicon-silicon interaction in bis(silylene)iron, disilanyliron, and bis(silyl)iron complexes",

abstract = "29Si NMR coupling constants in a disilanyliron complex CpFe(CO)2SiMe2SiMe(OtBu)2 (1: CP = η5C5H5), a bis(silylene)iron complex Cp(OC)Fe{SiMe2 ⋯ O(tBu) ⋯ SiMeOtBu)} (2), and a cis-bis(silyl)iron complex (OC)4Fe{SiMe2CH2CH2SiMePh} (3) were measured by the INEPT-INADE-QUATE technique. The coupling constant for 2 (28.6 Hz) is much smaller than that for 1 (128 Hz) with a direct Si-Si bond, but larger than that for 3 (2.7 Hz) where there is no direct Si-Si bond. Model calculations using the extended H{\"u}ckel method indicate that there is no direct bond between the two silicon atoms in the bis(silylene)iron complex Cp(OC)Fe{SiH2 ⋯ O(H) ⋯ SiH2}. This means that the coupling in 2 can be described as the sum of the two geminal couplings, 2J(SiFeSi) and 2J(SiOSi).",

author = "Keiji Ueno and Hiromi Tobita and Hiroshi Ogino",

year = "1992",

month = jun,

day = "2",

doi = "10.1016/0022-328X(92)80099-J",

language = "English",

volume = "430",

pages = "93--104",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "1",

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T1 - Silicon-silicon interaction in bis(silylene)iron, disilanyliron, and bis(silyl)iron complexes

AU - Ueno, Keiji

AU - Tobita, Hiromi

AU - Ogino, Hiroshi

PY - 1992/6/2

Y1 - 1992/6/2

N2 - 29Si NMR coupling constants in a disilanyliron complex CpFe(CO)2SiMe2SiMe(OtBu)2 (1: CP = η5C5H5), a bis(silylene)iron complex Cp(OC)Fe{SiMe2 ⋯ O(tBu) ⋯ SiMeOtBu)} (2), and a cis-bis(silyl)iron complex (OC)4Fe{SiMe2CH2CH2SiMePh} (3) were measured by the INEPT-INADE-QUATE technique. The coupling constant for 2 (28.6 Hz) is much smaller than that for 1 (128 Hz) with a direct Si-Si bond, but larger than that for 3 (2.7 Hz) where there is no direct Si-Si bond. Model calculations using the extended Hückel method indicate that there is no direct bond between the two silicon atoms in the bis(silylene)iron complex Cp(OC)Fe{SiH2 ⋯ O(H) ⋯ SiH2}. This means that the coupling in 2 can be described as the sum of the two geminal couplings, 2J(SiFeSi) and 2J(SiOSi).

AB - 29Si NMR coupling constants in a disilanyliron complex CpFe(CO)2SiMe2SiMe(OtBu)2 (1: CP = η5C5H5), a bis(silylene)iron complex Cp(OC)Fe{SiMe2 ⋯ O(tBu) ⋯ SiMeOtBu)} (2), and a cis-bis(silyl)iron complex (OC)4Fe{SiMe2CH2CH2SiMePh} (3) were measured by the INEPT-INADE-QUATE technique. The coupling constant for 2 (28.6 Hz) is much smaller than that for 1 (128 Hz) with a direct Si-Si bond, but larger than that for 3 (2.7 Hz) where there is no direct Si-Si bond. Model calculations using the extended Hückel method indicate that there is no direct bond between the two silicon atoms in the bis(silylene)iron complex Cp(OC)Fe{SiH2 ⋯ O(H) ⋯ SiH2}. This means that the coupling in 2 can be described as the sum of the two geminal couplings, 2J(SiFeSi) and 2J(SiOSi).

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