01928nas a2200229   4500008004100000022001400041245008600055210006900141260000800210300001600218490000700234520116200241100002001403700002501423700002301448700001901471700002701490700002701517700002101544700001801565856011501583       2022                        eng d  a0020-166900aFirst-row transition metal complexes of a phosphine-silylene- based hybrid ligand0 aFirstrow transition metal complexes of a phosphinesilylene based  cAUG  a13330-133410 v613 a<p>
	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.</p>
1 aAkhtar, Ruksana1 aKaulage, Sandeep, H.1 aSangole, Mayur, P.1 aTothadi, Srinu1 aParvathy, Parameswaran1 aParameswaran, Pattiyil1 aSingh, Kirandeep1 aKhan, Shabana  uhttps://library.ncl.res.in/content/first-row-transition-metal-complexes-phosphine-silylene-based-hybrid-ligand02167nas a2200289   4500008004100000022001400041245005500055210005200110260000800162490000700170520133100177653002301508653002401531653001901555653001101574653002201585100002001607700001901627700001501646700002301661700002401684700002101708700001701729700002401746700001901770856008801789       2024                        eng d  a0947-653900aTridentate NacNac tames T-shaped nickel(I) radical0 aTridentate NacNac tames Tshaped nickelI radical  cFEB0 v303 a<p>
	The reaction of a nickel(II) chloride complex containing a tridentate beta-diketiminato ligand with a picolyl group [2,6-iPr2-C6H3NC(Me)CHC(Me)NH(CH2py)]Ni(II)Cl (1)] with KSi(SiMe3)3 conveniently afforded a nickel(I) radical with a T-shaped geometry (2). The compound's metalloradical nature was confirmed through electron paramagnetic resonance (EPR) studies and its reaction with TEMPO, resulting in the formation of a highly unusual three-membered nickeloxaziridine complex (3). When reacted with disulfide and diselenide, the S-S and Se-Se bonds were cleaved, and a coupled product was formed through carbon atom of the pyridine-imine group. The nickel(I) radical activates dihydrogen at room temperature and atmospheric pressure to give the monomeric nickel hydride. A thermally stable, T-shaped, nickel(I) radical was straightforward obtained by reduction of a tridentate nacnac nickel(II) chloride with KSi(TMS)3. The metalloradical character of the compound was demonstrated by the formation of a highly unusual nickeloxaziridine complex upon addition of TEMPO. The Ni(I) species displays a rich chemistry towards activation S-S, and Se-Se bond leading to unusual C-C coupled product as well as dihydrogen activation at room temperature and atmospheric pressure to generate monomeric nickel hydride.+image</p>
10aC-C Bond formation10aHydrogen Activation10aMetalloradical10aNickel10aTridentate nacnac1 aPahar, Sanjukta1 aSharma, Vishal1 aRaj, Vipin1 aSangole, Mayur, P.1 aGeorge, Christy, P.1 aSingh, Kirandeep1 aVanka, Kumar1 aGonnade, Rajesh, G.1 aSen, Sakya, S.  uhttps://library.ncl.res.in/content/tridentate-nacnac-tames-t-shaped-nickeli-radical