Molecular Nitrides with Titanium and Group 13–15 Elements |
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| Authors: | María García‐Castro Dr. Avelino Martín Dr. Miguel Mena Dr. Carlos Yélamos Dr. |
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| Affiliation: | Departamento de Química Inorgánica, Universidad de Alcalá, 28871 Alcalá de Henares‐Madrid (Spain), Fax: (+34)?91‐8854683 |
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| Abstract: | Several heterometallic nitrido complexes were prepared by reaction of the imido–nitrido titanium complex [{Ti(η5‐C5Me5)(μ‐NH)}3(μ3‐N)] ( 1 ) with amido derivatives of Group 13–15 elements. Treatment of 1 with bis(trimethylsilyl)amido [M{N(SiMe3)2}3] derivatives of aluminum, gallium, or indium in toluene at 150–190 °C affords the single‐cube amidoaluminum complex [{(Me3Si)2N}Al{(μ3‐N)2(μ3‐NH)Ti3(η5‐C5Me5)3(μ3‐N)}] ( 2 ) or the corner‐shared double‐cube compounds [M(μ3‐N)3(μ3‐NH)3{Ti3(η5‐C5Me5)3(μ3‐N)}2] [M=Ga ( 3 ), In ( 4 )]. Complexes 3 and 4 were also obtained by treatment of 1 with the trialkyl derivatives [M(CH2SiMe3)3] (M=Ga, In) at high temperatures. The analogous reaction of 1 with [{Ga(NMe2)3}2] at 110 °C leads to [{Ga(μ3‐N)2(μ3‐NH)Ti3(η5‐C5Me5)3(μ3‐N)}2] ( 5 ), in which two [GaTi3N4] 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(SiMe3)2}2] in toluene at room temperature to give cube‐type complexes [M{(μ3‐N)2(μ3‐NH)Ti3(η5‐C5Me5)3(μ3‐N)}] [M=Ge ( 6 ), Sn ( 7 ), Pb ( 8 )]. Monitoring the reaction of 1 with [Sn{N(SiMe3)2}2] and [Sn(C5H5)2] by NMR spectroscopy allows the identification of intermediates [RSn{(μ3‐N)(μ3‐NH)2Ti3(η5‐C5Me5)3(μ3‐N)}] [R=N(SiMe3)2 ( 9 ), C5H5 ( 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(SiMe3)2}2] afford the corner‐shared double‐cube compound [Pb(μ3‐N)2(μ3‐NH)4{Ti3(η5‐C5Me5)3(μ3‐N)}2] ( 11 ). Analogous antimony and bismuth derivatives [M(μ3‐N)3(μ3‐NH)3{Ti3(η5‐C5Me5)3(μ3‐N)}2] [M=Sb ( 12 ), Bi ( 13 )] were obtained through the reaction of 1 with the tris(dimethylamido) reagents [M(NMe2)3]. Treatment of 1 with [AlCl2{N(SiMe3)2}(OEt2)] affords the precipitation of the singular aluminum–titanium square‐pyramidal aggregate [{{(Me3Si)2N}Cl3Al2}(μ3‐N)(μ3‐NH)2{Ti3(η5‐C5Me5)3(μ‐Cl)(μ3‐N)}] ( 14 ). The X‐ray crystal structures of 5 , 11 , 13 , 14 , and [AlCl{N(SiMe3)2}2] were determined. |
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| Keywords: | cage compounds cubanes main group elements nitrides titanium |
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