Carbonyl Insertions into Metal-Nitrogen Bonds of Group 4 Dialkylamido Complexes. X-ray Structure of Cp*(Me2N)2Ti[O(Me2N)C]W(CO)5

Mikhail Galakhov; Avelino Martín; Miguel Mena; Federico Palacios; Carlos Yélamos; Paul R. Raithby

doi:10.1021/om00001a022

Carbonyl Insertions into Metal-Nitrogen Bonds of Group 4 Dialkylamido Complexes. X-ray Structure of Cp*(Me₂N)₂Ti[O(Me₂N)C]W(CO)₅

Mikhail Galakhov, Avelino Martín, Miguel Mena, Federico Palacios, Carlos Yélamos, Paul R. Raithby

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

Abstract

[Cp*M(NMe₂)₃] [Cp* = η⁵-C₅Me₅; 1, M = Ti; 2, M = Zr] reacts with metal carbonyls, M'(CO)_n (n = 6, M' = Cr, Mo, W; n = 5, M' = Fe), to give the corresponding insertion products, Cp*(Me₂N)₂M[O(Me₂N)C]M'(CO)_n-1 (M = Ti; 3, M' = W; 4, M' = Mo; 5, M' = Cr; 6, M' = Fe; M = Zr; 7, M' = W; 8, M‘ = Mo; 9, M’ = Cr; 10, M' = Fe), in good yield. When complexes 3–5 were heated at 80 °C in toluene for several days, Cp*Ti(μ-NMe₂)₂[O(NMe₂)C]M'(CO)₃ (11, M' = W; 12, M' = Mo; 13, M' = Cr) were obtained. However, heating 6 under the same conditions gave Cp*(Me₂N)Ti[O(Me₂N)C]₂Fe(CO)₃ (14). Reactions of 12 with CO and Bu^t-NC have been carried out, giving compound 4 in the first case and Cp*(Me₂N)₂Ti[O(Me₂N)C]-Mo(CO)₃(CNBu^t)₂ (15) in the second. The structure of 3 has been proved unequivocally by a X-ray diffraction study (space group P2₁, a = 8.828(2) Å, b = 13.001(4) Å, c = 12.045(2) Å, β = 98.22(2)°, Z = 2, R₁ = 0.044 and wR₂= 0.109). 3 consists of two moieties, Cp*Ti(NMe₂)₂ and W(CO)₅, bridged by a [O(Me₂N)C] unit where the oxygen atom is bound to the oxophilic titanium atom, while the carbon is forming a Fischer carbene-like complex with tungsten.

Original language	English
Pages (from-to)	131-136
Number of pages	6
Journal	Organometallics
Volume	14
Issue number	1
DOIs	https://doi.org/10.1021/om00001a022
Publication status	Published - Jan 1995

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{88cc975070e044ed926f057b07ce57b5,

title = "Carbonyl Insertions into Metal-Nitrogen Bonds of Group 4 Dialkylamido Complexes. X-ray Structure of Cp*(Me2N)2Ti[O(Me2N)C]W(CO)5",

abstract = "[Cp*M(NMe2)3] [Cp* = η5-C5Me5; 1, M = Ti; 2, M = Zr] reacts with metal carbonyls, M'(CO)n (n = 6, M' = Cr, Mo, W; n = 5, M' = Fe), to give the corresponding insertion products, Cp*(Me2N)2M[O(Me2N)C]M'(CO)n-1 (M = Ti; 3, M' = W; 4, M' = Mo; 5, M' = Cr; 6, M' = Fe; M = Zr; 7, M' = W; 8, M{\textquoteleft} = Mo; 9, M{\textquoteright} = Cr; 10, M' = Fe), in good yield. When complexes 3–5 were heated at 80 °C in toluene for several days, Cp*Ti(μ-NMe2)2[O(NMe2)C]M'(CO)3 (11, M' = W; 12, M' = Mo; 13, M' = Cr) were obtained. However, heating 6 under the same conditions gave Cp*(Me2N)Ti[O(Me2N)C]2Fe(CO)3 (14). Reactions of 12 with CO and But-NC have been carried out, giving compound 4 in the first case and Cp*(Me2N)2Ti[O(Me2N)C]-Mo(CO)3(CNBut)2 (15) in the second. The structure of 3 has been proved unequivocally by a X-ray diffraction study (space group P21, a = 8.828(2) {\AA}, b = 13.001(4) {\AA}, c = 12.045(2) {\AA}, β = 98.22(2)°, Z = 2, R1 = 0.044 and wR2= 0.109). 3 consists of two moieties, Cp*Ti(NMe2)2 and W(CO)5, bridged by a [O(Me2N)C] unit where the oxygen atom is bound to the oxophilic titanium atom, while the carbon is forming a Fischer carbene-like complex with tungsten.",

author = "Mikhail Galakhov and Avelino Mart{\'i}n and Miguel Mena and Federico Palacios and Carlos Y{\'e}lamos and Raithby, \{Paul R.\}",

year = "1995",

month = jan,

doi = "10.1021/om00001a022",

language = "English",

volume = "14",

pages = "131--136",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "1",

}

TY - JOUR

T1 - Carbonyl Insertions into Metal-Nitrogen Bonds of Group 4 Dialkylamido Complexes. X-ray Structure of Cp*(Me2N)2Ti[O(Me2N)C]W(CO)5

AU - Galakhov, Mikhail

AU - Martín, Avelino

AU - Mena, Miguel

AU - Palacios, Federico

AU - Yélamos, Carlos

AU - Raithby, Paul R.

PY - 1995/1

Y1 - 1995/1

N2 - [Cp*M(NMe2)3] [Cp* = η5-C5Me5; 1, M = Ti; 2, M = Zr] reacts with metal carbonyls, M'(CO)n (n = 6, M' = Cr, Mo, W; n = 5, M' = Fe), to give the corresponding insertion products, Cp*(Me2N)2M[O(Me2N)C]M'(CO)n-1 (M = Ti; 3, M' = W; 4, M' = Mo; 5, M' = Cr; 6, M' = Fe; M = Zr; 7, M' = W; 8, M‘ = Mo; 9, M’ = Cr; 10, M' = Fe), in good yield. When complexes 3–5 were heated at 80 °C in toluene for several days, Cp*Ti(μ-NMe2)2[O(NMe2)C]M'(CO)3 (11, M' = W; 12, M' = Mo; 13, M' = Cr) were obtained. However, heating 6 under the same conditions gave Cp*(Me2N)Ti[O(Me2N)C]2Fe(CO)3 (14). Reactions of 12 with CO and But-NC have been carried out, giving compound 4 in the first case and Cp*(Me2N)2Ti[O(Me2N)C]-Mo(CO)3(CNBut)2 (15) in the second. The structure of 3 has been proved unequivocally by a X-ray diffraction study (space group P21, a = 8.828(2) Å, b = 13.001(4) Å, c = 12.045(2) Å, β = 98.22(2)°, Z = 2, R1 = 0.044 and wR2= 0.109). 3 consists of two moieties, Cp*Ti(NMe2)2 and W(CO)5, bridged by a [O(Me2N)C] unit where the oxygen atom is bound to the oxophilic titanium atom, while the carbon is forming a Fischer carbene-like complex with tungsten.

AB - [Cp*M(NMe2)3] [Cp* = η5-C5Me5; 1, M = Ti; 2, M = Zr] reacts with metal carbonyls, M'(CO)n (n = 6, M' = Cr, Mo, W; n = 5, M' = Fe), to give the corresponding insertion products, Cp*(Me2N)2M[O(Me2N)C]M'(CO)n-1 (M = Ti; 3, M' = W; 4, M' = Mo; 5, M' = Cr; 6, M' = Fe; M = Zr; 7, M' = W; 8, M‘ = Mo; 9, M’ = Cr; 10, M' = Fe), in good yield. When complexes 3–5 were heated at 80 °C in toluene for several days, Cp*Ti(μ-NMe2)2[O(NMe2)C]M'(CO)3 (11, M' = W; 12, M' = Mo; 13, M' = Cr) were obtained. However, heating 6 under the same conditions gave Cp*(Me2N)Ti[O(Me2N)C]2Fe(CO)3 (14). Reactions of 12 with CO and But-NC have been carried out, giving compound 4 in the first case and Cp*(Me2N)2Ti[O(Me2N)C]-Mo(CO)3(CNBut)2 (15) in the second. The structure of 3 has been proved unequivocally by a X-ray diffraction study (space group P21, a = 8.828(2) Å, b = 13.001(4) Å, c = 12.045(2) Å, β = 98.22(2)°, Z = 2, R1 = 0.044 and wR2= 0.109). 3 consists of two moieties, Cp*Ti(NMe2)2 and W(CO)5, bridged by a [O(Me2N)C] unit where the oxygen atom is bound to the oxophilic titanium atom, while the carbon is forming a Fischer carbene-like complex with tungsten.

UR - https://www.scopus.com/pages/publications/0001041104

U2 - 10.1021/om00001a022

DO - 10.1021/om00001a022

M3 - Article

AN - SCOPUS:0001041104

SN - 0276-7333

VL - 14

SP - 131

EP - 136

JO - Organometallics

JF - Organometallics

IS - 1

ER -

Carbonyl Insertions into Metal-Nitrogen Bonds of Group 4 Dialkylamido Complexes. X-ray Structure of Cp*(Me₂N)₂Ti[O(Me₂N)C]W(CO)₅

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