Molecular Nitrides with Titanium and Group 13–15 Elements

Several heterometallic nitrido complexes were prepared by reaction of the imido–nitrido titanium complex [{Ti(η 5 ‐C 5 Me 5 )(μ‐NH)} 3 (μ 3 ‐N)] ( 1 ) with amido derivatives of Group 13–15 elements. Treatment of 1 with bis(trimethylsilyl)amido [M{N(SiMe 3 ) 2 } 3 ] derivatives of aluminum, gallium, or indium in toluene at 150–190 °C affords the single‐cube amidoaluminum complex [{(Me 3 Si) 2 N}Al{(μ 3 ‐N) 2 (μ 3 ‐NH)Ti 3 (η 5 ‐C 5 Me 5 ) 3 (μ 3 ‐N)}] ( 2 ) or the corner‐shared double‐cube compounds [M(μ 3 ‐N) 3 (μ 3 ‐NH) 3 {Ti 3 (η 5 ‐C 5 Me 5 ) 3 (μ 3 ‐N)} 2 ] [M=Ga ( 3 ), In ( 4 )]. Complexes 3 and 4 were also obtained by treatment of 1 with the trialkyl derivatives [M(CH 2 SiMe 3 ) 3 ] (M=Ga, In) at high temperatures. The analogous reaction of 1 with [{Ga(NMe 2 ) 3 } 2 ] at 110 °C leads to [{Ga(μ 3 ‐N) 2 (μ 3 ‐NH)Ti 3 (η 5 ‐C 5 Me 5 ) 3 (μ 3 ‐N)} 2 ] ( 5 ), in which two [GaTi 3 N 4 ] cube‐type moieties are linked through a gallium–gallium bond. Complex 1 reacts with one equivalent of germanium, tin, or lead bis(trimethylsilyl)amido derivatives [M{N(SiMe 3 ) 2 } 2 ] in toluene at room temperature to give cube‐type complexes [M{(μ 3 ‐N) 2 (μ 3 ‐NH)Ti 3 (η 5 ‐C 5 Me 5 ) 3 (μ 3 ‐N)}] [M=Ge ( 6 ), Sn ( 7 ), Pb ( 8 )]. Monitoring the reaction of 1 with [Sn{N(SiMe 3 ) 2 } 2 ] and [Sn(C 5 H 5 ) 2 ] by NMR spectroscopy allows the identification of intermediates [RSn{(μ 3 ‐N)(μ 3 ‐NH) 2 Ti 3 (η 5 ‐C 5 Me 5 ) 3 (μ 3 ‐N)}] [R=N(SiMe 3 ) 2 ( 9 ), C 5 H 5 ( 10 )] in the formation of 7 . Addition of one equivalent of the metalloligand 1 to a solution of lead derivative 8 or the treatment of 1 with a half equivalent of [Pb{N(SiMe 3 ) 2 } 2 ] afford the corner‐shared double‐cube compound [Pb(μ 3 ‐N) 2 (μ 3 ‐NH) 4 {Ti 3 (η 5 ‐C 5 Me 5 ) 3 (μ 3 ‐N)} 2 ] ( 11 ). Analogous antimony and bismuth derivatives [M(μ 3 ‐N) 3 (μ 3 ‐NH) 3 {Ti 3 (η 5 ‐C 5 Me 5 ) 3 (μ 3 ‐N)} 2 ] [M=Sb ( 12 ), Bi ( 13 )] were obtained through the reaction of 1 with the tris(dimethylamido) reagents [M(NMe 2 ) 3 ]. Treatment of 1 with [AlCl 2 {N(SiMe 3 ) 2 }(OEt 2 )] affords the precipitation of the singular aluminum–titanium square‐pyramidal aggregate [{{(Me 3 Si) 2 N}Cl 3 Al 2 }(μ 3 ‐N)(μ 3 ‐NH) 2 {Ti 3 (η 5 ‐C 5 Me 5 ) 3 (μ‐Cl)(μ 3 ‐N)}] ( 14 ). The X‐ray crystal structures of 5 , 11 , 13 , 14 , and [AlCl{N(SiMe 3 ) 2 } 2 ] were determined.