Unsaturated binuclear cyclopentadienylmanganese carbonyl derivatives related to cymantrene

Xiuhui Zhang; Qian Shu Li; Yaoming Xie; R. Bruce King; Henry F. Schaefer

doi:10.1021/om7006453

Unsaturated binuclear cyclopentadienylmanganese carbonyl derivatives related to cymantrene

Xiuhui Zhang
, Qian Shu Li^*
, Yaoming Xie
, R. Bruce King
, Henry F. Schaefer

^*Corresponding author for this work

School of Chemistry and Chemical Engineering

Beijing Institute of Technology
South China Normal University
University of Georgia

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

24 Citations (Scopus)

Abstract

The cyclopentadienylmanganese carbonyls Cp₂Mn ₂(CO)_n(Cp = η⁵-C₅H₅; n = 5, 4, 3, 2) have been studied by density functional theory using the B3LYP and BP86 functionals. The pentacarbonyl Cp₂Mn₂(CO) ₅ is predicted to have a monobridged Cp₂Mn ₂(CO)₄(μ-CO) structure with an Mn-Mn distance of 2.804 Å(BP86), suggesting the single bond required for the 18-electron configuration. Its predicted infrared v(CO) frequencies agree very well with the transient v(CO) frequencies assigned to Cp₂Mn₂(CO) ₄(μ-CO) in the laser photolysis of CpMn(CO)₃ in hydrocarbon media. The tetracarbonyl Cp₂Mn₂(CO) ₄ has an Mn=Mn distance of 2.509 Å(BP86), indicative of an Mn=Mn double bond, but is thermodynamically unstable with respect to disproportionation into Cp₂Mn₂(CO)₅ + Cp ₂Mn₂(CO)₃. The tricarbonyl Cp ₂Mn₂(CO)₃ has three bridging CO groups with an Mn=Mn distance of 2.167 Å(BP86), suggesting an Mn≡Mn triple bond similar to the experimentally known structure of the stable (η⁵- Me₅C₅)₂Mn₂(CO)₃. A triplet structure for Cp₂Mn₂(CO)₂ with an Mn≡Mn triple bond (2.202 Å, BP86) is energetically preferred over a singlet structure with an Mn-Mn quadruple bond (2.067 Å, BP86).

Original language	English
Pages (from-to)	61-66
Number of pages	6
Journal	Organometallics
Volume	27
Issue number	1
DOIs	https://doi.org/10.1021/om7006453
Publication status	Published - 14 Jan 2008

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@article{f33df206dc67467aac2bbdf9322a7241,

title = "Unsaturated binuclear cyclopentadienylmanganese carbonyl derivatives related to cymantrene",

abstract = "The cyclopentadienylmanganese carbonyls Cp2Mn 2(CO)n(Cp = η5-C5H5; n = 5, 4, 3, 2) have been studied by density functional theory using the B3LYP and BP86 functionals. The pentacarbonyl Cp2Mn2(CO) 5 is predicted to have a monobridged Cp2Mn 2(CO)4(μ-CO) structure with an Mn-Mn distance of 2.804 {\AA}(BP86), suggesting the single bond required for the 18-electron configuration. Its predicted infrared v(CO) frequencies agree very well with the transient v(CO) frequencies assigned to Cp2Mn2(CO) 4(μ-CO) in the laser photolysis of CpMn(CO)3 in hydrocarbon media. The tetracarbonyl Cp2Mn2(CO) 4 has an Mn=Mn distance of 2.509 {\AA}(BP86), indicative of an Mn=Mn double bond, but is thermodynamically unstable with respect to disproportionation into Cp2Mn2(CO)5 + Cp 2Mn2(CO)3. The tricarbonyl Cp 2Mn2(CO)3 has three bridging CO groups with an Mn=Mn distance of 2.167 {\AA}(BP86), suggesting an Mn≡Mn triple bond similar to the experimentally known structure of the stable (η5- Me5C5)2Mn2(CO)3. A triplet structure for Cp2Mn2(CO)2 with an Mn≡Mn triple bond (2.202 {\AA}, BP86) is energetically preferred over a singlet structure with an Mn-Mn quadruple bond (2.067 {\AA}, BP86).",

author = "Xiuhui Zhang and Li, \{Qian Shu\} and Yaoming Xie and King, \{R. Bruce\} and Schaefer, \{Henry F.\}",

year = "2008",

month = jan,

day = "14",

doi = "10.1021/om7006453",

language = "English",

volume = "27",

pages = "61--66",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "1",

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TY - JOUR

T1 - Unsaturated binuclear cyclopentadienylmanganese carbonyl derivatives related to cymantrene

AU - Zhang, Xiuhui

AU - Li, Qian Shu

AU - Xie, Yaoming

AU - King, R. Bruce

AU - Schaefer, Henry F.

PY - 2008/1/14

Y1 - 2008/1/14

N2 - The cyclopentadienylmanganese carbonyls Cp2Mn 2(CO)n(Cp = η5-C5H5; n = 5, 4, 3, 2) have been studied by density functional theory using the B3LYP and BP86 functionals. The pentacarbonyl Cp2Mn2(CO) 5 is predicted to have a monobridged Cp2Mn 2(CO)4(μ-CO) structure with an Mn-Mn distance of 2.804 Å(BP86), suggesting the single bond required for the 18-electron configuration. Its predicted infrared v(CO) frequencies agree very well with the transient v(CO) frequencies assigned to Cp2Mn2(CO) 4(μ-CO) in the laser photolysis of CpMn(CO)3 in hydrocarbon media. The tetracarbonyl Cp2Mn2(CO) 4 has an Mn=Mn distance of 2.509 Å(BP86), indicative of an Mn=Mn double bond, but is thermodynamically unstable with respect to disproportionation into Cp2Mn2(CO)5 + Cp 2Mn2(CO)3. The tricarbonyl Cp 2Mn2(CO)3 has three bridging CO groups with an Mn=Mn distance of 2.167 Å(BP86), suggesting an Mn≡Mn triple bond similar to the experimentally known structure of the stable (η5- Me5C5)2Mn2(CO)3. A triplet structure for Cp2Mn2(CO)2 with an Mn≡Mn triple bond (2.202 Å, BP86) is energetically preferred over a singlet structure with an Mn-Mn quadruple bond (2.067 Å, BP86).

AB - The cyclopentadienylmanganese carbonyls Cp2Mn 2(CO)n(Cp = η5-C5H5; n = 5, 4, 3, 2) have been studied by density functional theory using the B3LYP and BP86 functionals. The pentacarbonyl Cp2Mn2(CO) 5 is predicted to have a monobridged Cp2Mn 2(CO)4(μ-CO) structure with an Mn-Mn distance of 2.804 Å(BP86), suggesting the single bond required for the 18-electron configuration. Its predicted infrared v(CO) frequencies agree very well with the transient v(CO) frequencies assigned to Cp2Mn2(CO) 4(μ-CO) in the laser photolysis of CpMn(CO)3 in hydrocarbon media. The tetracarbonyl Cp2Mn2(CO) 4 has an Mn=Mn distance of 2.509 Å(BP86), indicative of an Mn=Mn double bond, but is thermodynamically unstable with respect to disproportionation into Cp2Mn2(CO)5 + Cp 2Mn2(CO)3. The tricarbonyl Cp 2Mn2(CO)3 has three bridging CO groups with an Mn=Mn distance of 2.167 Å(BP86), suggesting an Mn≡Mn triple bond similar to the experimentally known structure of the stable (η5- Me5C5)2Mn2(CO)3. A triplet structure for Cp2Mn2(CO)2 with an Mn≡Mn triple bond (2.202 Å, BP86) is energetically preferred over a singlet structure with an Mn-Mn quadruple bond (2.067 Å, BP86).

UR - https://www.scopus.com/pages/publications/38749101952

U2 - 10.1021/om7006453

DO - 10.1021/om7006453

M3 - Article

AN - SCOPUS:38749101952

SN - 0276-7333

VL - 27

SP - 61

EP - 66

JO - Organometallics

JF - Organometallics

IS - 1

ER -

Unsaturated binuclear cyclopentadienylmanganese carbonyl derivatives related to cymantrene

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