@article {48215, title = {First-row transition metal complexes of a phosphine-silylene- based hybrid ligand}, journal = {Inorganic Chemistry}, volume = {61}, year = {2022}, month = {AUG}, pages = {13330-13341}, type = {Article}, abstract = {

We have prepared two new silylene-phosphine-based hybrid ligands Si{N(R)C6H4(PPh2)}{PhC((NBu)-Bu-t)(2)} [R = TMS {trimethylsilyl} (1) and TBDMS {tert-butyldimethylsilyl} (2)], which possess two donor sites. Furthermore, the treatment of the bidentate ligand 1 with base metal halides {FeBr2, CoBr2, NiCl(2)middotdme [nickel chloride(II) ethylene glycol dimethyl ether]} and 2 with NiBr(2)middotdme [nickel bromide(II) ethylene glycol dimethyl ether] afforded four-coordinate six-membered metal complexes 3-6, respectively, which feature coordination from both Si(II) and P(III) sites. Subsequently, complexes 3 [(FeBr2)Si{N(SiMe3)C6H4(PPh2)}{PhC((NBu)-Bu-t)(2)}], 4 [(CoBr2)Si{N(SiMe3)C6H4(PPh2)}{PhC((NBu)-Bu-t)(2)}], 5 [(NiCl2)Si{N(SiMe3)C6H4(PPh2)}{PhC((NBu)-Bu-t)(2)}], and 6 [(NiBr2)Si{N((SiBuMe2)-Bu-t)C6H4(PPh2)}{PhC((NBu)-Bu-t)(2)}] are studied for their redox and magnetic properties with the help of UV-vis spectroscopy, cyclic voltammetry, SQUID magnetometry, and theoretical calculations. Complexes 3-6 were found to display a paramagnetic behavior. All the compounds are well established by single-crystal X-ray diffraction studies.

}, issn = {0020-1669}, doi = {10.1021/acs.inorgchem.2c01233}, author = {Akhtar, Ruksana and Kaulage, Sandeep H. and Sangole, Mayur P. and Tothadi, Srinu and Parvathy, Parameswaran and Parameswaran, Pattiyil and Singh, Kirandeep and Khan, Shabana} } @article {49427, title = {Hybrid silylene-Pd catalyst: efficient C-N cross-coupling of sterically bulky amines and chiral amines}, journal = {Chemical Communications}, volume = {60}, year = {2024}, month = {SEP }, pages = {9958-9961}, type = {Article}, abstract = {

Herein, we report a catalytic system with N-heterocyclic silylene (NHSi)-phosphine-based hybrid bidentate ligands [PhC(NtBu)2SiN(PR2)(2,6-iPr2-C6H3)] and Pd(dba)2, which serves as an effective catalyst for C-N cross-coupling of a wide range of sterically bulky amines and optically active amines, which is challenging otherwise. Herein, we report a hybrid silylene-based bidentate ligand (SiNP)-Pd(0) catalytic system, which performs the C-N coupling of difficult substrates, e.g., sterically bulky amines and chiral amines.

}, issn = {1359-7345}, doi = {10.1039/d4cc03108c}, author = {Kaulage, Sandeep H. and Parvin, Nasrina and Khopade, Kishor V. and Khan, Shabana} } @article {49889, title = {Rongalite-promoted self-dimerization of 3-acylidene-2-oxindoles: a diastereoselective route to synthesis of bispirooxindoles}, journal = {Organic \& Biomolecular Chemistry}, volume = {23}, year = {2025}, month = {OCT}, pages = {8687-8694}, type = {Article}, abstract = {

A facile and efficient one-pot rongalite-mediated self-dimerization of 3-acylidene-2-oxindoles has been developed for the diastereoselective synthesis of highly functionalized dispirocyclopentanebisoxindoles. The reaction proceeds via a domino sequence involving intermolecular Michael addition followed by intramolecular aldol cyclization under basic conditions. Rongalite, an inexpensive and readily available reagent (similar to\$0.03 per g), plays a crucial role in promoting the transformation, offering significant advantages such as operational simplicity, step economy, scalability to gram-scale synthesis, and potential for post-functionalization. This methodology provides an efficient route to structurally complex oxindole frameworks with high stereocontrol, demonstrating broad synthetic utility.

}, issn = {1477-0520}, doi = {10.1039/d5ob01069a}, author = {Chaudhari, Suryakant S. and Nichinde, Chandrakant B. and Patil, Baliram R. and Girase, Amardipsing S. and Kaulage, Sandeep H. and Kinage, Anil K.} } @article {49868, title = {Silylene-copper(i) catalysis: regioselective protoboration of terminal alkynes}, journal = {Chemical Communications}, volume = {61}, year = {2025}, month = {DEC}, pages = {19652-19655}, type = {Article}, abstract = {

Herein, we report an efficient regioselective protoboration of the terminal alkynes catalyzed by newly synthesized silylene-copper(i)-aryl complexes. This method offers a broad substrate scope, good functional-group compatibility, and a gram-scale synthetic ability. The insight into the mechanistic cycle is also provided with the support of experimental and theoretical studies.

}, issn = {1359-7345}, doi = {10.1039/d5cc06125c}, author = {Kaulage, Sandeep H. and Shah, Brij Kumar and Panday, Rishukumar and Sharma, Himanshu and Vanka, Kumar and Khan, Shabana} }