Synthesis and reactivity of heteroleptic zinc(i) complexes toward heteroallenes

Abstract

Heteroleptic zinc(i) complexes Cp*Zn–ZnL1/2 were synthesized and reactions of Cp*Zn–ZnL22 with t-BuNCO and organoazides RN3 proceeded with insertion into the Zn–Zn bond and formation of novel zinc carbamate, bis-hexazene, triazenide, and azide complexes 4–7.

Dihydrogen Cleavage by a Zinc–Zinc Bond of a Heteroleptic Dizinc(I) Cation

“…The projection of the metal atom on the five-membered ring is displaced from its centroid by 0.243 and 0.148 Å, respectively. The Zn1–Cp*(centroid) distances in 2a (1.922 Å) and 2b (1.954 Å) are comparable to that in the heteroleptic zinc(I) complex [(HC{C(Me)NDipp} 2 )Zn–ZnCp*] (1.9215(3) Å) reported by Schulz and co-workers . The slipped η 5 -Cp* coordination agrees with the nonlinear Zn2–Zn1–Cp* bond angles with values of 165.5° in 2a and 168.5° in 2b .…”

“…Zinc(II) hydride complexes can be converted into the corresponding dinuclear zinc(I) complexes in what can be regarded as the reverse reaction of the dinuclear oxidative addition of dihydrogen. 23,24 Here, we report that a cationic dinuclear zinc(I) complex containing a Cp* and a chelating diamine ligand TMEDA or TEEDA (TMEDA = N,N,N′,N′-tetramethylethylenediamine; TEEDA = N,N,N′,N′tetraethylethylenediamine) is capable of cleaving dihydrogen. as β-diketiminate.…”

“…The Zn1−Cp*(centroid) distances in 2a (1.922 Å) and 2b (1.954 Å) are comparable to that in the heteroleptic zinc(I) complex [(HC{C(Me)NDipp} 2 )Zn− ZnCp*] (1.9215(3) Å) reported by Schulz and co-workers. 23 The slipped η 5 Reaction with Dihydrogen. Treatment of 2a with dihydrogen (ca.…”

“…While few examples of dihydrogen activation by zinc­(II) complexes are known, dinuclear zinc­(I) complexes including decamethyldizincocene [Zn 2 Cp* 2 ] (Cp* = η 5 -C 5 Me 5 ) reported by Carmona and co-workers have not been reported to react with dihydrogen. Zinc­(II) hydride complexes can be converted into the corresponding dinuclear zinc­(I) complexes in what can be regarded as the reverse reaction of the dinuclear oxidative addition of dihydrogen. , Here, we report that a cationic dinuclear zinc­(I) complex containing a Cp* and a chelating diamine ligand TMEDA or TEEDA (TMEDA = N , N , N′ , N ′ -tetramethylethylenediamine; TEEDA = N , N , N ′ , N ′ -tetraethylethylenediamine) is capable of cleaving dihydrogen.…”

Reactions of Zinc Hydride with Silylenes: From Oxidative Addition to Ligand Exchange Reactions

“…), only limited attention was drawn to the activation of metal hydrides. 17−19 Encouraged by our recent progress on the synthesis of heteroleptic Zn(I) complexes as well as of compounds containing Si−M bonds (M = Al, Ga), 20,21 we started to investigate reactions of organozinc hydrides and silylenes. We herein report on the synthesis and single crystal X-ray structures of novel heterobimetallic Si−Zn complexes.…”