Herein we present the first double deprotonation of acetonitrile (CH 3 CN) using two equivalents of a bimetallic iron-aluminium complex. The products of this reaction contain an exceeding simple yet rare [CHCN] 2À dianion moiety that bridges two metal fragments. DFT calculations suggest that the bonding to the metal centres occurs through heavily polarised covalent interactions. Mechanistic studies reveal the intermediacy of a monomeric [CH 2 CN] À complex, which has been characterised in situ. Our findings provide an important example in which a bimetallic metal complex achieves a new type of reactivity not previously encountered with monometallic counterparts. [1,2] The isolation of a [CHCN] 2À dianion through simple deprotonation of CH 3 CN also offers the possibility of establishing a broader chemistry of this motif.
Herein we present the first double deprotonation of acetonitrile (CH 3 CN) using two equivalents of a bimetallic iron-aluminium complex. The products of this reaction contain an exceeding simple yet rare [CHCN] 2À dianion moiety that bridges two metal fragments. DFT calculations suggest that the bonding to the metal centres occurs through heavily polarised covalent interactions. Mechanistic studies reveal the intermediacy of a monomeric [CH 2 CN] À complex, which has been characterised in situ. Our findings provide an important example in which a bimetallic metal complex achieves a new type of reactivity not previously encountered with monometallic counterparts. [1,2] The isolation of a [CHCN] 2À dianion through simple deprotonation of CH 3 CN also offers the possibility of establishing a broader chemistry of this motif.
Ti(IV) and Ti(III) complexes using the tBuPCP ligand have been synthesised (tBuPCP = C6H3-2,6-(CH2PtBu2)2). The [tBuPCP]Li synthon can be reacted with TiCl4(THF)2 to form (tBuPCP)TiCl3 (1) in limited yields due to significant reduction of the titanium synthon. The Ti(III) complex (tBuPCP)TiCl2 (2) has been further characterised. This can have half an equivalent of halide abstracted to form [{(tBuPCP)TiCl}2{μ-Cl}][B(C6F5)4] (3) and can also be methylated forming (tBuPCP)TiMe2 (4). All the Ti(III) complexes have been characterised using EPR and x-ray crystallography, giving insight into their electronic structure, which is further supported by DFT calculations.
Ti(IV) and Ti(III) complexes using the tBuPCP ligand have been synthesized (tBuPCP = C6H3-2,6-(CH2PtBu2)2). The [tBuPCP]Li synthon can be reacted with TiCl4(THF)2 to form (tBuPCP)TiCl3 (1) in limited yields due to significant reduction of the titanium synthon. The Ti(III) complex (tBuPCP)TiCl2 (2) has been further characterized. This can have half an equivalent of halide abstracted to form [{(tBuPCP)TiCl}2{μ-Cl}][B(C6F5)4] (3) and can also be methylated, forming (tBuPCP)TiMe2 (4). All the Ti(III) complexes have been characterized using EPR and X-ray crystallography, giving insight into their electronic structures, which are further supported by DFT calculations.
Herein we present the first double deprotonation of acetonitrile (CH3CN) using a bimetallic iron-aluminium complex. The products of this reaction contain an exceeding simple yet rare [CHCN]2– dianion moiety that bridges two metal fragments. DFT calculations suggest that the bonding to the metal centres is primarily ionic in nature. Mechanistic studies reveal the intermediacy of a monomeric [CH2CN]– complex, which has been characterised in-situ. Our findings provide an important example in which a bimetallic metal complex achieves a new type of reactivity not previously encountered with monometallic counterparts. The isolation of a [CHCN]2– dianion through simple deprotonation of CH3CN also offers the possibility of a establishing a broader chemistry of this motif.
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