Amidinato Germylene‐Zinc Complexes: Synthesis, Bonding, and Reactivity

Yadav, Sandeep; Kumar, Rohit; Raj, K. Vipin; Yadav, Prashant; Vanka, Kumar; Sen, Sakya S.

doi:10.1002/asia.202000807

Cited by 13 publications

(4 citation statements)

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“…( Me IPrCH) 2 Ge·ZnCl 2 ( 2 ) is a rare example of a molecular species with a localized germanium–zinc single bond and, to our knowledge, is the only Ge–Zn bonded species involving a three-coordinate Ge center. The Ge–Zn distance in 2 is 2.4315(10) Å and is slightly elongated with respect to the Ge–Zn distance [2.3839(11) Å] found in Power’s four-coordinate Ge complex [(Ar Me6 ) 2 Ge(Et)-ZnEt], derived from the reaction of the germylene Ar Me6 2 Ge with ZnEt 2 (Ar Me6 = 2,6-Mes 2 C 6 H 3 ; Mes = 2,4,6-Me 3 C 6 H 2 ) .…”

Section: Results and Discussionmentioning

confidence: 91%

Zinc-Mediated Transmetalation as a Route to Anionic N-Heterocyclic Olefin Complexes in the p-Block

2021

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Anionic N-heterocyclic olefins (aNHOs) are suited well for the stabilization of low-coordinate inorganic complexes, due to their steric tunability and strong σand π-electron donating abilities. In this study, the new two-coordinate zinc complex ( Me IPrCH) 2 Zn ( Me IPrCH = [(MeCNDipp) 2 CCH] − , Dipp = 2,6diisopropylphenyl) is shown to participate in a broad range of metathesis reactions with main group element-based halides and hydrides. In the case of the group 14 halides, Cl 2 E•dioxane (E = Ge and Sn), transmetalation occurs to form dinuclear propellane-shaped cations, [( Me IPrCHE) 2 (μ-Cl)] + , while the aNHO-capped phosphine ligand Me IPrCH-PPh 2 is obtained when ( Me IPrCH) 2 Zn is combined with ClPPh 2 . Lastly, ZnH 2 elimination drives transmetalation between ( Me IPrCH) 2 Zn and hydroboranes and hydroalumanes, leading to Lewis acidic aNHO-supported -boryl and -alane products.

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Section: Results and Discussionmentioning

confidence: 91%

Zinc-Mediated Transmetalation as a Route to Anionic N-Heterocyclic Olefin Complexes in the p-Block

2021

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“…Very recently, we have reported a germylene-zinc adduct and its reaction with sulfur, where the sulfur atom inserts into the Ge!Zn bond leading to Ge=S coordinated zinc complexes. [17] Inspired from this reaction, we wonder whether sulfur can insert into the ZnÀ Et bond of 1 and afford NHC supported zinc thiolate complexes, which have a modicum of precedence. [18] A further impetus comes from the synthetic difficulties associated with the accessing of zinc sulfide nanoparticles as mentioned by Rivard and coworkers.…”

Section: Resultsmentioning

confidence: 99%

Six‐Membered NHC Stabilized Monomeric Zinc Complexes

et al. 2023

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This paper describes the rare use of a 6‐membered saturated N‐heterocyclic carbene (NHC) known as 1,3‐di(2,6‐diisopropylphenyl) tetrahydropyrimidine‐2‐ylidene (abbreviated as 6‐SIDipp) as a ligand in zinc chemistry. We report on the investigation of the reactions between 6‐SIDipp and ZnX2, which resulted in a range of new monomeric 6‐SIDipp⋅ZnX2 complexes (X=Et (1), Cl (2), Br (3), and I (4)). We also prepared a new NHC zinc complex where the two substituents of the zinc atom are different, 6‐SIDipp⋅Zn(Et)Br (7) through the reaction of the proligand [6‐SIDippH]Br with ZnEt2. We have observed that the reactions of complex 1 with sulfur and HBpin led to the removal of the ZnEt2 moiety, resulting in the formation of a C=S double bond and a B−H activation product, respectively. Lastly, the reaction of 1 with five‐membered NHCs led to the exchange of carbene and the formation of either 5‐IDipp⋅ZnEt2 (8) or 5‐SIDipp⋅ZnEt2 (9).

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“…The NPA charge analysis suggests that 2 contains a highly polar, covalent metal-metal single bond Ge δÀ -Zn δ + where the more electronegative germanium center forms the negative end (natural charges of 0.77 e (Ge) and 1.25 e (Zn)) (Figure 2). The Wiberg Bond Index (WBI) of 0.40 for the GeÀ Zn bond in 2 is significantly lower than those in germanium(II) stabilized zinc halide complexes [PhC(NtBu) 2 Ge {N(SiMe 3 ) 2 }!ZnX 2 ] 2 (X = Br (III) and I (IV)) [45] and zincagermylene Ge(TBoN)(ZnL*) (II) with Ge!Zn (0.61) and GeÀ Zn (0.68-0.77) bonds. [31] This lower WBI value also shows the highly polar nature of the GeÀ Zn interaction in 2 compared to those in compounds II-IV.…”

Section: Resultsmentioning

confidence: 99%

Heterobimetallic Hydrides with a Germanium(II)‐Zinc Bond

Mahawar

Rajeshkumar

Maron

et al. 2023

Chemistry A European J

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In the presence of TMEDA (TMEDA=N,N,N’,N’‐tetramethylethylenediamine), zinc dihydride reacted with germanium(II) compounds (BDI−H)Ge (1) and [(BDI)Ge][B(3,5‐(CF3)2C6H3)4] (3) (BDI‐H = HC{(C=CH2)(CMe)(NAr)2}, BDI = [HC(CMeNAr)2]; Ar = 2,6‐iPr2C6H3) by formal insertion of the germanium(II) center into the Zn−H bond of polymeric [ZnH2]n to give neutral and cationic zincagermane with a H−Ge‐Zn−H core [(BDI−H)Ge(H)‐(H)Zn(tmeda)] (2) and [(BDI)Ge(H)‐(H)Zn(tmeda)][B(3,5‐(CF3)2C6H3)4] (4), respectively. Compound 2 eliminated [ZnH2] giving diamido germylene 1 at 60 °C. Compound 2 and deuterated analogue 2‐d2 exchanged with [ZnH2]n and [ZnD2]n in the presence of TMEDA to give a mixture of 2 and 2‐d2. Compounds 2 and 4 reacted with carbon dioxide (1 bar) at room temperature to form zincagermane diformate [(BDI−H)Ge(OCHO)‐(OCHO)Zn(tmeda)] (5) and formate bridged digermylene [({BDI}Ge)2(μ‐OCHO)]+[B(C6H3(CF3)2)4] (6) along with zinc formate [(tmeda)Zn(μ‐OCHO)3Zn(tmeda)][B(C6H3(CF3)2)4] (7), respectively. The hydridic nature of the Ge−H and Zn−H bonds in 2 and 4 was probed by reactions with Brönsted and Lewis acids.

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Amidinato Germylene‐Zinc Complexes: Synthesis, Bonding, and Reactivity

Abstract: Dedicated to Professor Samaresh Bhattacharya on the occasion of his 60th birthday.

Cited by 13 publications

References 50 publications

Zinc-Mediated Transmetalation as a Route to Anionic N-Heterocyclic Olefin Complexes in the p-Block

Zinc-Mediated Transmetalation as a Route to Anionic N-Heterocyclic Olefin Complexes in the p-Block

Six‐Membered NHC Stabilized Monomeric Zinc Complexes

Heterobimetallic Hydrides with a Germanium(II)‐Zinc Bond

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