TY - JOUR
T1 - Insertion and cleavage reactions of [closo-3,1,2-Ta(NMe2)3-(C2B9H 11)] with nitriles, phenols and thiols; structural characterisation of N,N-dimethylamidinate ligands
AU - Broder, Charlotte K.
AU - Goeta, Andres E.
AU - Howard, Judith A.K.
AU - Hughes, Andrew K.
AU - Johnson, Andrew L.
AU - Malget, John M.
AU - Wade, Ken
PY - 2000/12/1
Y1 - 2000/12/1
N2 - The tantalum complex [closo-3,1,2-Ta(NMe2)3(C2B9H n)] underwent insertion into the NC bond of acetonitrile and p-fluorobenzonitrile to give the N,N-dimethylacetamidinate complex [closo-3,1,2-Ta{N=C(Me)NMe2}3(C2B 9H11)], andp-nuoro-N,N-dimethylbenzamidinate, [closo-3,1,2-Ta{N=C(C6H4F)NMe2} 3(C2B9H11)], respectively. Attempted re-crystallisation of the latter from chlorinated solvents led to [closo-3,1,2-Ta{N=C(C6H4F)NMe2} 2Cl(C2B9H11)], in which one amidinate ligand has been replaced by a chloride. [closo-3,1,2-Ta(NMe2)3(C2B9H 11)] reacts with cyclohexylisocyanide to give [Ta(NMe2)2{r)2-N(Cy)CNMe2}(C 2B9H11)]. The structures of the novel JV.W-dialkylamidinate complexes have been determined by single crystal X-ray diffraction, and reveal the extensive délocalisation and strong n-donor character of the amidinate ligands. The M-N bonds of [cloJo-3,1,2-Ta(NMe2)3(C2B9H) 11] are cleaved by protic reagents, and it reacts with 2,6-dimethyIphenol to give [c/oio-3,1,2-Ta(OC6H3Me2-2, 6)3(C2B9H11)] and with benzenethiol to give the charge-compensated complex [closo-3-Ta(SC6H5)4(9-NHMe 2-l,2-C2B9H10)] where the β-boron of the C2B3 face bears a NHMe2+ substituent. The structures of the last two compounds have also been determined.
AB - The tantalum complex [closo-3,1,2-Ta(NMe2)3(C2B9H n)] underwent insertion into the NC bond of acetonitrile and p-fluorobenzonitrile to give the N,N-dimethylacetamidinate complex [closo-3,1,2-Ta{N=C(Me)NMe2}3(C2B 9H11)], andp-nuoro-N,N-dimethylbenzamidinate, [closo-3,1,2-Ta{N=C(C6H4F)NMe2} 3(C2B9H11)], respectively. Attempted re-crystallisation of the latter from chlorinated solvents led to [closo-3,1,2-Ta{N=C(C6H4F)NMe2} 2Cl(C2B9H11)], in which one amidinate ligand has been replaced by a chloride. [closo-3,1,2-Ta(NMe2)3(C2B9H 11)] reacts with cyclohexylisocyanide to give [Ta(NMe2)2{r)2-N(Cy)CNMe2}(C 2B9H11)]. The structures of the novel JV.W-dialkylamidinate complexes have been determined by single crystal X-ray diffraction, and reveal the extensive délocalisation and strong n-donor character of the amidinate ligands. The M-N bonds of [cloJo-3,1,2-Ta(NMe2)3(C2B9H) 11] are cleaved by protic reagents, and it reacts with 2,6-dimethyIphenol to give [c/oio-3,1,2-Ta(OC6H3Me2-2, 6)3(C2B9H11)] and with benzenethiol to give the charge-compensated complex [closo-3-Ta(SC6H5)4(9-NHMe 2-l,2-C2B9H10)] where the β-boron of the C2B3 face bears a NHMe2+ substituent. The structures of the last two compounds have also been determined.
UR - http://www.scopus.com/inward/record.url?scp=0001807439&partnerID=8YFLogxK
U2 - 10.1039/b004862n
DO - 10.1039/b004862n
M3 - Article
AN - SCOPUS:0001807439
SN - 1470-479X
SP - 3526
EP - 3533
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 20
ER -