Synthesis and molecular structure of the first organometallic nitride cubane: [{Ti(η⁵-C₅Me₅)}₄(µ₃-N)₄]

Abstract

The ammonolysis of [ T I ( ~~-C ~M ~~) ( N M ~~) ~I at 90 "C affords the nitride complex [{Ti(y5-C,Me,)},(~L,-N)41; the X-ray crystal structure analysis shows a Ti4N4 core clearly similar to the structural motif of cubic titanium nitride.

Titanium Alkali Metal Nitrido Complexes

“…[1,2] Prior to our work, Roesky et al had described the imido ± nitrido complex [{Ti(h 5 -C 5 Me 5 )(m-NH)} 3 (m 3 -N)] (1) obtained by the ammonolysis of [{Ti(h 5 -C 5 Me 5 )Me 3 ]. [3] We have recently showed that 1 is capable of displacing labile ligands (mesitylene, carbonyls) coordinated to Group 6 metals to give d 0 ± d 6 azaheterometallocubane compounds.…”

[{Ti(η5-C5Me5)(μ-NH)}3(μ3-N)]: An Efficient Entry to Single and Double Cube-Type Nitrido Complexes

“…[3] As well as this triruthenium cluster, the dinuclear ruthenium tetrahydride [{(h 5 -C 5 Me 5 )Ru} 2 (m-H) 4 ] (2) has been shown to provide an active species for multimetallic activation and to undergo cleavage of various types of bonds such as C(sp 2 ) À H, Si À H, and P À C(aryl) bonds under mild conditions. [5] A resonance signal due to the hydrogen atom attached to the a-carbon (C1) appeared at d 9.33 in the 1 H NMR spectrum. We report herein an unprecedented type of selective carbon-Àcarbon bond cleavage of norbornadiene by the dinuclear ruthenium tetrahydride complex 2.…”

“…

Group 4 tetrametallic derivatives of the formula [(ML n ) 4 (m 3 -E) 4 ] with cube-type cores remain extremely rare and are limited to halide-bridged [{TiL} 4 (m 3 -Cl) 4 ] (L h 8 -C 8 H 8 , [1] Me 3 [2] ), chalcogenide-bridged [{Ti(h 5 -C 5 H 4 R)} 4 (m 3 -S) 4 ], [3] and imido-bridged [{Ti(h 5 -C 5 H 5 )} 4 (m 3 -NSnMe 3 ) 4 ] complexes. [4] Our first contributions in this field were the preparation of the singular nitrido and alkylidyne complexes [{Ti(h 5 -C 5 Me 5 )(m 3 -E)} 4 ] (E N [5] , CH [6] ), which contained an almost perfect Ti 4 E 4 cube. A possible synthetic strategy to access this type of compounds would involve the incorporation of different metal complex fragments in a cuboidal core such as [Ti 3 (m-NH) 3 (m 3 -N)], [7] in a similar way to that reported for [M 3 (m-S) 3 (m 3 -S)] species.

…”

[{Ti(η5-C5Me5)(μ-NH)}3(μ3-N)]: An Efficient Entry to Single and Double Cube-Type Nitrido Complexes

“…[4] Our first contributions in this field were the preparation of the singular nitrido and alkylidyne complexes [{Ti(h 5 -C 5 Me 5 )(m 3 -E)} 4 ] (E N [5] , CH [6] ), which contained an almost perfect Ti 4 E 4 cube. A possible synthetic strategy to access this type of compounds would involve the incorporation of different metal complex fragments in a cuboidal core such as [Ti 3 (m-NH) 3 (m 3 -N)], [7] in a similar way to that reported for [M 3 (m-S) 3 (m 3 -S)] species.…”

“…2 (J C,H 151.0 Hz, C4) for the carbon atoms of the ruthenacycle, and the chemical shifts were comparable to those observed in the related h 5 -cyclohexadienylruthenium complexes. [5] A resonance signal due to the hydrogen atom attached to the a-carbon (C1) appeared at d 9.33 in the 1 H NMR spectrum. The two hydrogen atoms on C6 are diastereotopic and their resonance signals appeared at d 2.38 and d 3.18.…”