02325nas a2200241 4500008004100000022001400041245010100055210006900156260006900225300001000294490000800304520143300312653001201745653003401757653002301791653003901814653001201853653002201865100001801887700002501905700002401930856012901954 2014 eng d a0010-854500aContemporary avenues in catalytic P-H bond addition reaction: a case study of hydrophosphination0 aContemporary avenues in catalytic PH bond addition reaction a ca aPO BOX 564, 1001 LAUSANNE, SWITZERLANDbELSEVIER SCIENCE SAcAPR a52-730 v2653 a

Remarkable advances and current state-of-the-art developments in catalytic hydrophosphination of alkenes and alkynes are reviewed. The challenges in constructing a C P bond with a special emphasis on metal catalysed (asymmetric) hydrophosphination are highlighted. Only those systems that unambiguously proceed via P H bond addition across a C-C/X (X = O, N, S) multiple bond have been covered in this overview. Reviewed examples support the assumption that either strongly chelating ligands or reaction products that act as ligands, enhance the rate of hydrophosphination. The asymmetric variant of this transformation allows installation of p-chiral [enantiomeric excess (ee) up to 82%] as well as C-chiral (ee up to 99%) centres. The limited spectroscopic, mechanistic data and OFT calculations point at two distinctly different mechanisms. In case of hydrophosphination, the metal undergoes oxidative addition and reductive elimination steps (in general), thus changing the oxidation state from M(0) to M(II) and back to M(0). Whereas in asymmetric hydrophosphination it is proposed that the oxidation state of the metal remains unaltered throughout the catalytic cycle. The examples described in this overview showcase the real power of catalytic hydrophosphination in constructing various phosphorus compounds, which may initiate a new era in organo-phosphorus chemistry. (C) 2014 Elsevier B.V. All rights reserved.

10aAlkynes10aAsymmetric hydrophosphination10aHydrophosphination10aMetal catalyzed hydrophosphination10aOlefins10aP-H bond addition1 aKoshti, Vijay1 aGaikwad, Shahaji, R.1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/contemporary-avenues-catalytic-p-h-bond-addition-reaction-case-study-hydrophosphination-001821nas a2200229 4500008004100000022001400041245010000055210006900155260006700224300000800291490000700299520096500306653002201271653003101293653002301324653002301347653001901370100002501389700002401414700002401438856012901462 2014 eng d a0887-624X00aPd-Phosphinesulfonate bravely battles the ``vinyl halide insertion copolymerization'' barricade0 aPdPhosphinesulfonate bravely battles the vinyl halide insertion  a111 RIVER ST, HOBOKEN 07030-5774, NJ USAbWILEY-BLACKWELLcJAN a1-60 v523 a

This overview provides insights into the current state-of-the-art solutions to insertion copolymerization of functional olefinic monomers. The challenges in insertion copolymerization of functional olefinic monomers, with a special emphasis on vinyl halides, are highlighted. The crucial design of the Pd-phosphinesulfonate [Pd(PO)] enables up to 3.6 mol % incorporation of vinyl fluoride (VF) in an ethylene-VF copolymerization reaction. In a significant development, insertion copolymerization of industrially relevant functional olefin, that is, vinyl chloride (VC), was unambiguously ascertained, and a detectable amount of VC (0.4 mol %) was incorporated (at the chain end). In a detailed investigation, the in situ existence of (PO)PdH species during the polymerization was revealed, and it was demonstrated that these are indeed responsible for VC incorporation. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1-6

10afunctional olefin10ainsertion copolymerization10apalladium catalyst10aphosphinesulfonate10avinyl chloride1 aGaikwad, Shahaji, R.1 aDeshmukh, Satej, S.1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/pd-phosphinesulfonate-bravely-battles-vinyl-halide-insertion-copolymerization-barricade-001755nas a2200193 4500008004100000022001400041245008200055210006900137260007100206300001200277490000600289520103400295100002501329700002401354700002401378700002401402700002401426856011101450 2015 eng d a2161-165300aInsertion copolymerization of difunctional polar vinyl monomers with ethylene0 aInsertion copolymerization of difunctional polar vinyl monomers  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcSEP a933-9370 v43 a

A single-step synthesis, structural characterization and application of a neutral, acetonitrile ligated, palladium-phosphinesulfonate complex [{P<\^>O}PdMe(L)] (P<\^>O = K-2-P,O Ar2PC6H4SO2O with Ar = 2-MeOC6H4; L = CH3CN) (3) in coordination/insertion copolymerization of ethylene with difunctional olefin is investigated. In a significant development, complex 3 was found to catalyze insertion copolymerization of industrially relevant 1,1-disubstituted difunctional vinyl monomers for the first time. Thus, insertion copolymerization of ethyl-2-cyanoacrylate (ECA or super glue) and trifluoromethyl acrylic acid (TFMAA) with ethylene produced the corresponding copolymers with 6.5% ECA and 3% TFMAA incorporation. Increasing the concentration of difunctional olefins led to higher incorporation but at the expense of lower activities. These observations indicate that complex 3 tolerates difunctional vinyl monomers and provides direct access to difunctional polyolefins that have not been attempted before.

1 aGaikwad, Shahaji, R.1 aDeshmukh, Satej, S.1 aGonnade, Rajesh, G.1 aRajamohanan, P., R.1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/insertion-copolymerization-difunctional-polar-vinyl-monomers-ethylene-100588nas a2200133 4500008004100000022002000041245010400061210006900165250002400234260001500258100002400273700002500297856013200322 2016 eng d aWO2016038631 A100aMetal phosphine-sulfonate acetonitrile complex for insertion copolymerization of functional olefins0 aMetal phosphinesulfonate acetonitrile complex for insertion copo aC07F9/50, C07F15/00 aIndiacMAR1 aChikkali, Samir, H.1 aGaikwad, Shahaji, R. uhttps://library.ncl.res.in/content/metal-phosphine-sulfonate-acetonitrile-complex-insertion-copolymerization-functional-olefins02517nas a2200205 4500008004100000245015200041210006900193260000800262300001600270490000700286520173400293100002102027700001702048700002302065700002502088700002202113700002402135700002402159856012802183 2017 eng d00aH-Bonding assisted self-assembly of anionic and neutral ligand on metal: a comprehensive strategy to mimic ditopic ligands in olefin polymerization0 aHBonding assisted selfassembly of anionic and neutral ligand on  cOCT a12448-124560 v563 aSelf-assembly of two neutral ligands on a metal to mimic bidentate ligand coordination has been frequently encountered in the recent past, but self-assembly of an anionic ligand on a metal template alongside a neutral ligand remains an elusive target. Such a self-assembly is hampered by additional complexity, wherein a highly negatively charged anion can form intermolecular hydrogen bonding with the supramolecular motif, leaving no scope for self-assembly with neutral ligand. Presented here is the self-association of anionic ligand 3-ureidobenzoic acid (2a) and neutral ligand 1-(3-(diphenylphosphanyl)phenyl)urea (1a) on a metal template to yield metal complex [{COOC6H4-NH(CO)NH2}{Ph2PC6H4NH(CO)NH2}PdMeDMSO] (4a). The identity of 4a was established by NMR and mass spectroscopy. Along the same lines, 3-(3-phenylureido)benzoic acid (2b) and 1-(3-(diphenylphosphanyl)phenyl)-3-phenylurea (1b) self-assemble on a metal template to produce palladium complex [{COOC6H4NH(CO)NHPh}{Ph2PC6H4NH(CO)NHPh}PdMePy] (5c). The existence of 5c was confirmed by Job plot, 1-2D NMR spectroscopy, deuterium labeling, IR spectroscopy, UV-vis spectroscopy, model complex synthesis, and DFT calculations. These solution and gas phase investigations authenticated the presence of intramolecular hydrogen bonding between hydrogen's of 1b and carbonyl oxygen of 2b. The generality of the supramolecular approach has been validated by preparing six complexes from four monodentate ligands, and their synthetic utility was demonstrated in ethylene polymerization. Complex 4a was found to be the most active, leading to the production of highly branched polyethylene with a molecular weight of 55700 g/mol and melting temperature of 112 degrees C.1 aMote, Nilesh, R.1 aPatel, Ketan1 aShinde, Dinesh, R.1 aGaikwad, Shahaji, R.1 aKoshti, Vijay, S.1 aGonnade, Rajesh, G.1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/h-bonding-assisted-self-assembly-anionic-and-neutral-ligand-metal-comprehensive-strategy02658nas a2200205 4500008004100000245010100041210006900142260000800211300001400219490000700233520190800240100002502148700002402173700002202197700002002219700002402239700003502263700002402298856013002322 2017 eng d00aReactivity of difunctional polar monomers and ethylene copolymerization: a comprehensive account0 aReactivity of difunctional polar monomers and ethylene copolymer cAUG a5748-57580 v503 aA comprehensive picture of insertion of 1,1-disubstituted difunctional olefins, their ability to double the functional group density at the same level of incorporation as that of monofunctional olefin, and copolymerization with ethylene has been demonstrated. Exposure of a palladium complex [{P boolean AND O}PdMe(L)] (P boolean AND O = kappa(2)-P,O-Ar2PC6H4SO2O with Ar = 2-MeOC6H4.; L = C2H6OS) to methyl 2-acetamidoacrylate (MAAA) revealed slight preference for 1,2-insertion over 2,1-insertion (1.0:0.7). In contrast, insertion of electron-deficient 2-(trifluoromethyl)acrylic acid (TFMAA) unveiled selective 2,1-insertion {via [(P boolean AND O)PdC5H6F3O2] (11)1. The unstable intermediate 11 undergoes beta-hydride and beta-fluoride elimination to produce subsequent insertion and elimination products. The identity of elimination products (E/Z)-2-trifluoromethyl)but-2-enoic acid [17(E/Z)] and 2-(difluoromethylene)butanoic acid (13) was fully established by 1-2D NMR spectroscopy. These insertion experiments, taken together with insertion rates, suggest that MAAA and TFMAA. are amenable to insertion. Polymerization of ethylene with MAAA, TFMAA, acetamidoacrylic acid, 2-bromoacrylic acid, dimethyl allylmalonate, and allylmalonic acid was catalyzed by [{P boolean AND O}PdMe(L)] (L = C2H3N) (S.ACN), and the highest incorporation of 11.8% was observed for dimethyl allylmalonate (DMAM). The changes in the surface properties of the copolymers after incorporation of difunctional olefins were evaluated by measuring the water contact angle. Copolymer with highest (11.8% of DMAM) incorporation revealed a reduced water contact angle of 76 degrees. These findings demonstrate that 1,1-disubstituted difunctional olefins are amenable to polymerization, and incorporation of difunctional olefins In polyethylene backbone leads to the production of relatively hydrophilic polyethylene copolymers.1 aGaikwad, Shahaji, R.1 aDeshmukh, Satej, S.1 aKoshti, Vijay, S.1 aPoddar, Suparna1 aGonnade, Rajesh, G.1 aRajamohanan, Pattuparambil, R.1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/reactivity-difunctional-polar-monomers-and-ethylene-copolymerization-comprehensive-account02077nas a2200181 4500008004100000245010200041210006900143260000800212300001400220490000800234520140600242100002401648700002501672700002201697700002101719700002401740856013101764 2017 eng d00aSynthesis of meta-substituted monodentate phosphinite ligands and implication in hydroformylation0 aSynthesis of metasubstituted monodentate phosphinite ligands and cAUG a1143-11520 v1293 aSynthesis of meta-substituted phosphinite ligands 3,3'-(methoxyphosphanediyl) bis(N, N-diethylaniline) (4a) and methoxybis(3-methoxyphenyl) phosphane (4b), in high yields, has been demonstrated. Typical phosphorus chemical shift between 110-120 ppm, appearance of methoxy protons and corresponding carbon, as well as ESI-MS spectra unambiguously confirmed the existence of phosphinite ligands 4a and 4b. To demonstrate the synthetic usefulness of 4a and 4b, these ligands were tested in the rhodium catalyzed hydroformylation of 1-octene. The diethylamine substituted ligand 4a was found to be highly active, whereas 4bwas less reactive but revealed slightly better regioselectivity of 62% under optimized conditions. Additionally, 4a and 4b were found to catalyze the hydroformylation of styrene, 1-undecenol and 1,1-disubstituted functional olefin, methyl methacrylate. Both the ligands displayed excellent conversion of styrene, and 4b revealed an excellent branch selectivity of 75%. Although 1-undecenol proved to be amenable to hydroformylation (85-90% conversion to aldehyde), both the ligands failed to discriminate between the linear and branched products. Substrate methyl methacrylate proved to be highly challenging and reduced conversion (between 33-42%) was observed under optimized conditions. Ligand 4a was found to be highly selective towards linear aldehyde (81% linear selectivity).1 aDeshmukh, Satej, S.1 aGaikwad, Shahaji, R.1 aPandey, Swechchha1 aMali, Pramod, S.1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/synthesis-meta-substituted-monodentate-phosphinite-ligands-and-implication-hydroformylation02237nas a2200205 4500008004100000022001400041245011100055210006900166260000800235300001400243490000600257520151000263100002401773700002501797700002101822700001401843700002401857700002401881856012601905 2019 eng d a2470-134300aNeutral imino-methyl benzenesulfonate-ligated Pd(II) complexes and implications in ethylene polymerization0 aNeutral iminomethyl benzenesulfonateligated PdII complexes and i cMAY a9502-95110 v43 a

A reaction between sodium 2-formylbenzenesulfonate and aniline revealed the near-quantitative (91%) formation of sodium-2-((phenylimino)methyl)benzenesulfonate L1. The identity of L1 was unambiguously ascertained using spectroscopic and analytical methods. The scope of this methodology was widened and various electron-donating amines were treated with sodium 2-formylbenzenesulfonate, and a small library of 6 imine ligands L2-L6 was generated. When L2 was treated with [(COD)PdMeCI], instead of the anticipated [L2PdMe(DMSO)] complex, the formation of [(DMSO)(2)Pd2Cl2Me2] Pd Dim was observed. Nevertheless, the desired imino-methyl benzenesulfonate-ligated palladium complex [L2PdMe(Lu)] C1 was obtained by in situ abstraction of chloride and addition of bulky 2,6-lutidine as the donor group. The observation of characteristic Pd-Me protons at 0.06 ppm and the corresponding carbon at -8.1 ppm indicated the formation of C1. These 1D NMR observations were corroborated by 2D C-H correlation spectra and mass analysis, and the existence of C1 was unambiguously ascertained. Along the same lines, L4 and L5 were treated with a palladium precursor to produce [L4/SPdMe(Lu)]-type complexes C2-C3 in 55-84% yield, and their identity was established by using a combination of spectroscopic tools, analytical methods, and single-crystal X-ray diffraction. The synthetic utility of C1-C3 has been demonstrated by utilizing these complexes in the insertion polymerization of ethylene to polyethylene.

1 aDeshmukh, Satej, S.1 aGaikwad, Shahaji, R.1 aMote, Nilesh, R.1 aManod, M.1 aGonnade, Rajesh, G.1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/neutral-imino-methyl-benzenesulfonate-ligated-pdii-complexes-and-implications-ethylene02037nas a2200289 4500008004100000022001400041245013000055210006900185260000800254300001400262490000700276520106100283653002601344653003101370653001201401653001401413653001701427100002501444700001701469700002401486700002101510700002701531700002401558700002101582700002401603856012001627 2020 eng d a2192-650600aPalladium-catalyzed insertion of ethylene and 1,1-disubstituted difunctional olefins: an experimental and computational study0 aPalladiumcatalyzed insertion of ethylene and 11disubstituted dif cJUN a1200-12090 v853 a

Insertion or coordination copolymerization of ethylene with di-substituted olefins is challenging and the choice of di-substituted mono-functional olefin versus di-substituted di-functional olefin (DDO) appears to be decisive. Here we show that DDO-inserted species are amenable to ethylene insertion and polymerization. DDOs such as 2-acetamidoacrylic acid (AAA), methyl 2-acetamidoacrylate (MAAA), and ethyl 2-cyanoacrylate (ECA) were treated with palladium complex [{P perpendicular to O}PdMe(L)] (P perpendicular to O=kappa(2)-P,O-Ar2PC6H4SO2O with Ar=2-MeOC6H4; L=C2H6OS) and the existence of respective insertion intermediates in moderate yield (up to 37 %) was established. These intermediates were exposed to ethylene and corresponding ethylene-inserted products were isolated and characterized. A careful comparison with three model compounds confirmed ethylene insertion and polymerization. Thus, the combined experimental and computational investigations show that DDO-inserted species can undergo ethylene insertion and polymerization.

10aHomogeneous catalysis10ainsertion copolymerization10aOlefins10aPalladium10aPolyethylene1 aGaikwad, Shahaji, R.1 aPatel, Ketan1 aDeshmukh, Satej, S.1 aMote, Nilesh, R.1 aBirajdar, Rajkumar, S.1 aPandole, Satish, P.1 aChugh, Jeetender1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/palladium-catalyzed-insertion-ethylene-and-11-disubstituted-difunctional-olefins02236nas a2200253 4500008004100000022001400041245008000055210006900135260000900204300001200213490000700225520142200232653001001654653002201664653002901686653001701715653001701732100002401749700002501773700002401798700002401822700002401846856011201870 2020 eng d a1861-472800aPd-iminocarboxylate complexes and their behavior in ethylene polymerization0 aPdiminocarboxylate complexes and their behavior in ethylene poly cFEB  a398-4050 v153 a

Designing co-catalyst-free late transition metal complexes for ethylene polymerization is a challenging task at the interface of organometallic and polymer chemistry. Herein, a set of new, co-catalyst-free, single-component catalytic systems for ethylene polymerization have been unraveled. Treatment of anthranilic acid with various aldehydes produced four iminocarboxylate ligands (L1-L4) in very good to excellent yield (75-92 %). The existence of 2-((2-methoxybenzylidene)amino) benzoic acid (L1) has been unambiguously demonstrated using NMR spectroscopy, MS and single-crystal X-ray diffraction. A neutral Pd-iminocarboxylate complex [{N O}PdMe(L1)] (N O=kappa(2)-N,O-ArCHNC6H4CO2 with Ar=2-MeOC6H4) C1 was prepared by treating stoichiometric amount of L1.Na with palladium precursor. The identity of C1 was confirmed by 1-2D NMR spectroscopy and single-crystal X-ray diffraction studies. Along the same lines, palladium complexes C2-C4 were prepared from ligands L2-L4 respectively. In-situ high-pressure NMR investigations revealed that these Pd complexes are amenable to ethylene insertion and undergo facile beta-H elimination to produce propylene. These palladium complexes were then evaluated in ethylene polymerization reaction and various reaction parameters were screened. When C1-C4 were exposed to ethylene pressures of 10-50 bar, formation of low-molecular-weight polyethylene was observed.

10aimine10aImine-carboxylate10aInsertion polymerization10aPd complexes10aPolyethylene1 aDeshmukh, Satej, S.1 aGaikwad, Shahaji, R.1 aGonnade, Rajesh, G.1 aPandole, Satish, P.1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/pd-iminocarboxylate-complexes-and-their-behavior-ethylene-polymerization02478nas a2200193 4500008004100000022001400041245012500055210006900180260000900249300001400258490000700272520177700279100002102056700002502077700000502102700002402107700002402131856012902155 2021 eng d a1477-922600aControlled di-lithiation enabled synthesis of phosphine-sulfonamide ligands and implications in ethylene oligomerization0 aControlled dilithiation enabled synthesis of phosphinesulfonamid cMAR  a3717-37230 v503 a

Catalyst design for ethylene oligomerization has attracted significant interest. Herein, we report the synthesis of phosphine-sulfonamide-derived palladium complexes and examine their performance in ethylene oligomerization. Arresting a dilithiation intermediate of N-(2-bromophenyl)-4-methylbenzenesulfonamide (1) at -84 degrees C selectively produced N-(2-(bis(2-methoxyphenyl)phosphanyl)phenyl)-4-methylbenzenesulfonamide (L1A). However, the same reaction at -41 degrees C delivered a different ligand; 2-(bis(2-methoxyphenyl)phosphanyl)-4-methyl-N-phenylbenzenesulfonamide (L2A). The generality of our strategy has been demonstrated by preparing N-(2-(diphenylphosphanyl)phenyl)-4-methylbenzenesulfonamide (L1B) and 2-(diphenylphosphanyl)-4-methyl-N-phenylbenzenesulfonamide (L2B). Subsequently, L1A and L1B were treated with a palladium precursor to yield 5-membered complexes C1 and C2, respectively. In contrast, L2A upon treatment with palladium produced a 6-membered metal complex C3. Thus, a small library of 7 palladium complexes (C1-C7) were synthesized by varying the donor moiety (pyridine, DMSO, and acetonitrile). The identity of palladium complexes was unambiguously ascertained using a combination of spectroscopic and analytical methods, including single-crystal X-ray diffraction. The performance of the complexes C1-C7 was investigated in ethylene oligomerization and almost all of them were found to be active. The resultant ethylene oligomers were characterized using H-1 and C-13 NMR, MALDI-ToF-MS, and GPC. Detailed screening of reaction parameters revealed 100 degrees C and 40 bars ethylene to be optimal conditions. Complex C5 outperformed other complexes and produced ethylene oligomers with a molecular weight of 1000-1900 g mol(-1).

1 aMote, Nilesh, R.1 aGaikwad, Shahaji, R.1 a1 aGonnade, Rajesh, G.1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/controlled-di-lithiation-enabled-synthesis-phosphine-sulfonamide-ligands-and-implications