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 - http://www.scopus.com/inward/record.url?scp=0001041104&partnerID=8YFLogxK
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 -