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

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.

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

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

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-radical02220nas a2200289 4500008004100000245011500041210006900156260000800225300000900233490000700242520124100249100002501490700002301515700002601538700001701564700002301581700002101604700002901625700002801654700001701682700002101699700002101720700002401741700002001765700002201785856012301807 2026 eng d00aSmallest acyclic tricationic molecule containing a Bis(phosphine)-stabilized low-valent triantimony-based Unit0 aSmallest acyclic tricationic molecule containing a Bisphosphines cMAR a26970 v173 a

Element-element bonded multiply charged cationic species are well known as dimers or small cyclic oligomers in the condensed phase. However, the smallest acyclic version, a trinuclear unit possessing greater than a monocationic charge, has remained elusive. Here we introduce a bis(phosphine) supported low valent triantimony-based tricationic compound as a new entrant in this field. Structural elucidation and electronic understanding reveal a W-shaped tricationic unit comprising of a three-center four-electron sigma-bonded triantimony moiety that is terminally capped by bis(phosphine) ligands, with the central antimony atom having two lone pairs of electrons. The unique counter trianion [Sb(O)2(OTf)4]3- (OTf = CF3SO3) possesses reactive polar Sb delta+-O delta- bonds, the structure of which is determined from single crystal X-ray diffraction analysis. The ensemble of reactive molecular fragments found in this highly charged antimony-based compound makes it thermally unstable. Nonetheless, this fully characterized fleeting species shows a diverse reactivity profile, advancing the isolation of various novel antimony compounds, including the formation of a distinct low-valent antimony-cobalt carbonyl cluster.

1 aMukherjee, Nilanjana1 aPeerless, Benjamin1 aNadurata, Vincent, L.1 aKumar, Vikas1 aSangole, Mayur, P.1 aSingh, Kirandeep1 aWiedemann, Haakon, T. A.1 aKay, Christopher, W. M.1 aKruk, Robert1 aWeigend, Florian1 aDehnen, Stefanie1 aGonnade, Rajesh, G.1 aYildiz, Cem, B.1 aMajumdar, Moumita uhttps://library.ncl.res.in/content/smallest-acyclic-tricationic-molecule-containing-bisphosphine-stabilized-low-valent