The Ti=NNMe(2) group of Cp*Ti{MeC(N(i)Pr)(2)}(NNMe(2)) undergoes 1,2-addition with Si-Cl and reversible addition with Si-H bonds of RSiH(2)X (R = Ph or Bu; X = Cl or H). Labeling studies show that the so-formed silylhydrazide-hydride products react with primary silanes or H(2)via σ-bond metathesis between Ti-H and either Si-H or H-H.

We report a combined experimental and computational comparative study of the reactions of the homologous titanium dialkyl- and diphenylhydrazido and imido compounds Cp*Ti{MeC(N(i)Pr)(2)}(NNR(2)) (R = Me (1) or Ph (2)) and Cp*Ti{MeC(N(i)Pr)(2)}(NTol) (3) with silanes, halosilanes, alkyl halides and [Et(3)NH][BPh(4)]. Compound 1 underwent reversible Si-H 1,2-addition to Ti=N(α) with RSiH(3) (experimental ΔH ca. -17 kcal mol(-1)), and irreversible addition with PhSiH(2)X (X = Cl, Br). DFT found that the reaction products and certain intermediates were stabilised by β-NMe(2) coordination to titanium. The Ti-D bond in Cp*Ti{MeC(N(i)Pr)(2)}(D){N(NMe(2))SiD(2)Ph} underwent σ-bond metathesis with BuSiH(3) and H(2). Compound 1 reacted with RR'SiCl(2) at N(α) to transfer both Cl atoms to Ti; 2 underwent a similar reaction. Compound 3 did not react with RSiH(3) or alkyl halides but formed unstable Ti=N(α) 1,2-addition or N(α) protonation products with PhSiH(2)X or [Et(3)NH][BPh(4)]. Compound 1 underwent exclusive alkylation at N(β) with RCH(2)X (R = H, Me or Ph; X = Br or I) whereas protonation using [Et(3)NH][BPh(4)] occurred at N(α). DFT studies found that in all cases electrophile addition to N(α) (with or without NMe(2) chelation) was thermodynamically favoured compared to addition to N(β).

We report a comprehensive combined experimental and DFT investigation of the synthesis, molecular and electronic structures, and reactivity of terminal hydrazido complexes with CO 2 , CS 2 , isocyanates, and isothiocyanates. Reaction of Cp*Ti{MeC(N i Pr) 2 }(N t Bu) with hydrazines R 1 R 2 NNH 2 gave the structurally characterized series of hydrazides Cp*Ti{MeC(N i Pr) 2 }(NNR 1 R 2 ) (R 1 = Ph, R 2 = Ph (13), Me (14); R 1 = R 2 = Me (15)). The energetics of this imide/hydrazine exchange reaction, as well as the electronic and molecular structures of 13-15, have been evaluated by DFT and compared with those of their methyl and phenyl imido counterparts. Reaction of 13-15 with CO 2 or CS 2 gave TidN R cycloaddition products of the type Cp*Ti{MeC(N i Pr) 2 }{N(NR 2 )C(E)E} (R = Ph, Me; E = O, S) and, in the case of CO 2 , cycloaddition-insertion products Cp*Ti{MeC-(N i Pr) 2 }{OC(O)N(NR 2 )C(O)O}, in which 2 equivs of CO 2 had effectively inserted into TidN R . Reaction of 13 with isocyanates and isothiocyanates also gave stable cycloaddition products. Cp*Ti{MeC(N i Pr) 2 }{N(NPh 2 )C(NTol)O} reacted further with CO 2 to give a mixed cycloaddition-insertion product. The t BuNCO moiety in Cp*Ti{MeC(N i Pr) 2 }{N(NPh 2 )C(N t Bu)O} could be displaced by CO 2 or TolNCO. In contrast, the reactions of 15 are dominated by cycloaddition-elimination reactions. Reaction with t BuNCO or Ar 0 NCO (2 equivs) gave t BuNCNNMe 2 or the heterocycle 1,2,4-N(Me) 2 NC(NAr 0 )N(Ar 0 )C(O), respectively, along with [Cp*Ti{MeC-(N i Pr) 2 }(μ-O)] 2 . With TolNCO (2 equivs), Cp*Ti{MeC(N i Pr) 2 }{OC(NNMe 2 )N(Tol)C(NTol)O} was formed via a series of cycloaddition-elimination and cycloaddition-insertion steps. The energetics and mechanisms of the cycloaddition, cycloaddition-insertion, and cycloaddition-extrusion processes of various model imido and hydrazido complexes have been investigated using DFT. In the latter (metathesis) reactions, the reaction outcomes depend on a delicate balance of the relative affinities of NR or NNR 2 for the metal center or the organic fragment (CO, CS, or RNC).

We report a detailed study of the reactions of the Ti=NNCPh2 alkylidene hydrazide functional group in [Cp*Ti{MeC(NiPr)2}(NNCPh2)] (8) with a variety of unsaturated and saturated substrates. Compound 8 was prepared from [Cp*Ti{MeC(NiPr)2}(NtBu)] and Ph2CNNH2. DFT calculations were used to determine the nature of the bonding for the Ti=NNCPh2 moiety in 8 and in the previously reported [Cp2Ti(NNCPh2)(PMe3)]. Reaction of 8 with CO2 gave dimeric [(Cp*Ti{MeC(NiPr)2}{μ-OC(NNCPh2)O})2] and the "double-insertion" dicarboxylate species [Cp*Ti-{MeC(NiPr)2}{OC(O)N(NCPh2)C(O)O}] through an initial [2+2] cycloaddition product [Cp*Ti{MeC(NiPr)2}{N(NCPh2)C(O)O}], the congener of which could be isolated in the corresponding reaction with CS2. The reaction with isocyanates or isothiocyanates tBuNCO or ArNCE (Ar = Tol or 2,6-C6 H3 iPr2 ; E = O, S) gave either complete NNCPh2 transfer, [2+2] cycloaddition to Ti=Nα or single- or double-substrate insertion into the Ti=Nα bond. The treatment of 8 with isonitriles RNC (R = tBu or Xyl) formed σ-adducts [Cp*Ti{MeC(NiPr)2}(NNCPh2)(CNR)]. With Ar(F5)CCH (Ar(F5)=C6F5) the [2+2] cycloaddition product [Cp*Ti{MeC(NiPr)2}{N(NCPh2)C(Ar(F5))C(H)}] was formed, whereas with benzonitriles ArCN (Ar = Ph or Ar(F5)) two equivalents of substrate were coupled in a head-to-tail manner across the Ti=Nα bond to form [Cp*Ti{MeC(NiPr)2}{N(NCPh2)C(Ar)NC(Ar)N}]. Treatment of 8 with RSiH3 (R = aryl or Bu) or Ph2SiH2 gave [Cp*Ti{MeC(NiPr)2}{N(SiHRR')N(CHPh2)}] (R' = H or Ph) through net 1,3-addition of Si-H to the N-N=CPh2 linkage of 8, whereas reaction with PhSiH2X (X = Cl, Br) led to the Ti=Nα 1,2-addition products [Cp*Ti{MeC(NiPr)2}(X){N(NCPh2)SiH2Ph}].