01772nas a2200265 4500008004100000022001400041245007500055210006900130260000900199300001400208490000700222520099600229653000801225653001601233653001401249653002001263653000901283100001901292700001701311700001501328700002001343700001701363700001901380856010701399 2020 eng d a1861-472800aAmidinato germylene-zinc complexes: synthesis, bonding, and reactivity0 aAmidinato germylenezinc complexes synthesis bonding and reactivi cOCT  a3116-31210 v153 a

Despite the explosive growth of germylene compounds as ligands in transition metal complexes, there is a modicum of precedence for the germylene zinc complexes. In this work, the synthesis and characterization of new germylene zinc complexes [PhC(NtBu)(2)Ge{N(SiMe3)(2)}-> ZnX2](2)(X= Br (2) and I (3)) supported by (benz)-amidinato germylene ligands are reported. The solid-state structures of2and3have been validated by single-crystal X-ray diffraction studies, which revealed the dimeric nature of the complexes, with distorted tetrahedral geometries around the Ge and Zn center. DFT calculations reveal that the Ge-Zn bonds in2and3are dative in nature. The reaction of2with elemental sulfur resulted in the first structurally characterized germathione stabilized ZnBr(2)complexes PhC(NtBu)(2)Ge(=S){N(SiMe3)(2)}-> ZnBr2(5). Therefore, the Ge=S in5is in-between Ge-S single and Ge=S double bond length, owing to the coordination of a sulfur lone pair of electrons to ZnBr2.

10aDFT10aGermathione10aGermylene10aX-ray Structure10azinc1 aYadav, Sandeep1 aKumar, Rohit1 aRaj, Vipin1 aYadav, Prashant1 aVanka, Kumar1 aSen, Sakya, S. uhttps://library.ncl.res.in/content/amidinato-germylene-zinc-complexes-synthesis-bonding-and-reactivity02181nas a2200301 4500008004100000022001400041245012700055210006900182260000800251300001200259490000700271520122000278653001201498653001401510653001101524653001401535653002001549100001701569700001901586700001801605700001901623700002501642700002201667700001701689700002401706700001901730856013001749 2020 eng d a1861-472800aTale of biphenyl and terphenyl substituents for structurally diverse ketiminato magnesium, calcium and germanium complexes0 aTale of biphenyl and terphenyl substituents for structurally div cMAR a820-8270 v153 a

In this paper, we have used two N,O-ketiminato ligands (L1 and L2) with biphenyl and terphenyl substituent on the nitrogen atom. Deprotonation of L1 with KN(SiMe3)(2) and subsequent reaction with MgI2 led to a homoleptic dinuclear magnesium complex (1) with a Mg2O2 four-membered ring. Deprotonation with nBuLi and subsequent reaction with MgI2 afforded a unusual dinuclear magnesium complex (2) with a Mg2O2 ring. Extension of the ligand for calcium resulted in a trinuclear calcium complex (3) with six four-membered Ca2O2 rings. We could not isolate any chelating complex when L2 was used as a ligand, and only oxygen bound magnesium (4) and calcium (5) adducts were isolated. DFT studies were performed to understand this dissimilar behavior. More diverse results were obtained when lithiated L1 and L2 were treated with germanium dichloride. We were able to stabilize a monomeric germylene monochloride (7) with L1. However, with L2, an unusual ligand scrambling, and a C-C coupling take place, leading to the formation of a secondary carbocation with GeCl3- as a counter-anion (8). Besides, a germanium dichloride adduct (9) bound to the oxygen center of the ligand was obtained as the minor product.

10acalcium10aGermylene10aligand10aMagnesium10aX-ray Structure1 aKumar, Rohit1 aYadav, Sandeep1 aGour, Kritika1 aSangtani, Ekta1 aDash, Soumya, Ranjan1 aRaja, Abhishekram1 aVanka, Kumar1 aGonnade, Rajesh, G.1 aSen, Sakya, S. uhttps://library.ncl.res.in/content/tale-biphenyl-and-terphenyl-substituents-structurally-diverse-ketiminato-magnesium-calcium01252nas a2200241 4500008004100000022001400041245008400055210006900139260000800208490000700216520048300223653002300706653003000729653001400759653001400773653001600787100002300803700002000826700002700846700001900873700001900892856009900911 2025 eng d a1434-194800aC=C insertion over N=C=O of allyl isocyanate into the Ge-Si bond of a germylene0 aCC insertion over NCO of allyl isocyanate into the GeSi bond of  cSEP0 v283 a

Two isocyanates are reacted with the germylene, PhC(NtBu)(2)Ge-Si(SiMe3)(3) (1). Phenyl isocyanate undergoes catalytic cyclotrimerization with 1 leading to 1,3,5-triphenyl isocyanurate (2), while allyl isocyanate undergoes both cyclotrimerization and the C=C bond insertion between the Ge-Si bond. The constitution of 3 is determined by single-crystal X-ray studies. The contrasting reactivity pattern is explained by comprehensive density functional theory studies.

10aCyclotrimerization10aDensity functional theory10aGermylene10aInsertion10aisocyanates1 aAjithkumar, V., S.1 aKhilari, Nripen1 aGhanwat, Pratiksha, B.1 aKoley, Debasis1 aSen, Sakya, S. uhttps://library.ncl.res.in/content/cc-insertion-over-nco-allyl-isocyanate-ge-si-bond-germylene01776nas a2200253 4500008004100000245009800041210006900139260000900208490000700217520092400224653001401148653002501162653001501187653002301202100001801225700002101243700002501264700002901289700002201318700001701340700001901357700001901376856012701395 2025 eng d00aGermylene mediated reductive C-C and C-N coupling of an isocyanide and its device application0 aGermylene mediated reductive CC and CN coupling of an isocyanide cFEB 0 v643 a

We have demonstrated a unique reductive coupling of 4-iodophenyl isocyanide, facilitated by a perimidine-based N-heterocyclic germylene (NHGe), which yields a bis-spirogerma compound featuring simultaneous C-C and C-N bond formation. This reaction, which leads to the oxidation of germanium from +2 to +4, represents a significant departure from previously documented isocyanide-germylene interactions. The product exhibits extensive conjugation across its bicyclic C4Ge2N2 framework, conferring distinct photophysical properties, including prominent orange luminescence in both solution and solid states. The photophysical properties are supported by the TD-DFT calculations confirming an n ->pi* transition. The potential application of this compound in optoelectronic devices, particularly as a hole transport layer in PbS quantum dot solar cells, is also explored, with promising preliminary results.

10aGermylene10ahole transport layer10aIsocyanide10areductive coupling1 aGour, Kritika1 aPramanik, Debjit1 aDash, Soumya, Ranjan1 aShinde, Dipak, Dattatray1 aVenugopal, Geethu1 aVanka, Kumar1 aRath, Arup, K.1 aSen, Sakya, S. uhttps://library.ncl.res.in/content/germylene-mediated-reductive-c-c-and-c-n-coupling-isocyanide-and-its-device-application