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Didier Bourissou - One of the best experts on this subject based on the ideXlab platform.

  • Chelating Assistance of P–C and P–H Bond Activation at Palladium and Nickel: Straightforward Access to Diverse Pincer Complexes from a Diphosphine–Phosphine Oxide
    2016
    Co-Authors: Eric J. Derrah, Carmen Martin, Sonia Mallet-ladeira, Karinne Miqueu, Ghenwa Bouhadir, Didier Bourissou
    Abstract:

    The diphosphine–phosphine oxide (DPPO) {[o-i-Pr2P-(C6H4)]2P­(O)­Ph} (1) reacts with [Ni­(cod)2] (cod = 1,4-cyclooctadiene) to give the diphosphine–phosphide oxide κP,P(O),P pincer complex 3. According to DFT calculations, the Ph–P­(O) bond activation involves a three-center P,Cipso,Ni transition state. Reaction of the DPPO ligand 1 with [(nbd)­Pd­(ma)] (nbd = 2,5-norbornadiene and ma = maleic anhydride) affords the [(DPPO)­Pd­(ma)] complex 4. Upon heating, the ma coligand is displaced and the κP,P(O),P palladium pincer complex 2 is obtained. The dinuclear complex {(DPPO)­[Pd­(ma)]2} (6) has also been authenticated. X-ray diffraction analysis showed an original situation in which the oxygen atom of the central phosphine oxide moiety bridges the two palladium centers. Addition of trifluoromethanesulfonic acid to DPPO 1 affords the trifunctional phosphine–phosphine oxide–Phosphonium Derivative 7. Upon reaction with [Pd2(dba)3], the palladium hydride κP,O(P),P pincer complex 8 is cleanly formed as the result of P+–H bond activation. Complex 8 is readily deprotonated by DBU (DBU = 1,8-diazabicycloundec-7-ene), and spontaneous oxidative addition of the Ph–P­(O) bond gives the diphosphine–phosphide oxide κP,P(O),P pincer complex 2. Conversely, addition of trifluoromethanesulfonic acid on 2 does not give back the palladium hydride 8 but leads to the diphosphine–hydroxy phosphine κP,P(OH),P pincer complex 9

Bourissou D. - One of the best experts on this subject based on the ideXlab platform.

  • Chelating assistance of P-C and P-H bond activation at palladium and nickel: Straightforward access to diverse pincer complexes from a diphosphine-phosphine oxide
    'American Chemical Society (ACS)', 2013
    Co-Authors: Derrah E.j., Martin C., Mallet-ladeira Sonia, Miqueu Karinne, Bouhadir G., Bourissou D.
    Abstract:

    cited By 19International audienceThe diphosphine-phosphine oxide (DPPO) [o-i-Pr2P-(C 6H4)]2P(O)Ph (1) reacts with [Ni(cod) 2] (cod = 1,4-cyclooctadiene) to give the diphosphine-phosphide oxide κP,P(O),P pincer complex 3. According to DFT calculations, the Ph-P(O) bond activation involves a three-center P,Cipso,Ni transition state. Reaction of the DPPO ligand 1 with [(nbd)Pd(ma)] (nbd = 2,5-norbornadiene and ma = maleic anhydride) affords the [(DPPO)Pd(ma)] complex 4. Upon heating, the ma coligand is displaced and the κP,P(O),P palladium pincer complex 2 is obtained. The dinuclear complex (DPPO)[Pd(ma)]2 (6) has also been authenticated. X-ray diffraction analysis showed an original situation in which the oxygen atom of the central phosphine oxide moiety bridges the two palladium centers. Addition of trifluoromethanesulfonic acid to DPPO 1 affords the trifunctional phosphine-phosphine oxide-Phosphonium Derivative 7. Upon reaction with [Pd 2(dba)3], the palladium hydride κP,O(P),P pincer complex 8 is cleanly formed as the result of P+-H bond activation. Complex 8 is readily deprotonated by DBU (DBU = 1,8- diazabicycloundec-7-ene), and spontaneous oxidative addition of the Ph-P(O) bond gives the diphosphine-phosphide oxide κP,P(O),P pincer complex 2. Conversely, addition of trifluoromethanesulfonic acid on 2 does not give back the palladium hydride 8 but leads to the diphosphine-hydroxy phosphine κP,P(OH),P pincer complex 9. © 2013 American Chemical Society

Eric J. Derrah - One of the best experts on this subject based on the ideXlab platform.

  • Chelating Assistance of P–C and P–H Bond Activation at Palladium and Nickel: Straightforward Access to Diverse Pincer Complexes from a Diphosphine–Phosphine Oxide
    2016
    Co-Authors: Eric J. Derrah, Carmen Martin, Sonia Mallet-ladeira, Karinne Miqueu, Ghenwa Bouhadir, Didier Bourissou
    Abstract:

    The diphosphine–phosphine oxide (DPPO) {[o-i-Pr2P-(C6H4)]2P­(O)­Ph} (1) reacts with [Ni­(cod)2] (cod = 1,4-cyclooctadiene) to give the diphosphine–phosphide oxide κP,P(O),P pincer complex 3. According to DFT calculations, the Ph–P­(O) bond activation involves a three-center P,Cipso,Ni transition state. Reaction of the DPPO ligand 1 with [(nbd)­Pd­(ma)] (nbd = 2,5-norbornadiene and ma = maleic anhydride) affords the [(DPPO)­Pd­(ma)] complex 4. Upon heating, the ma coligand is displaced and the κP,P(O),P palladium pincer complex 2 is obtained. The dinuclear complex {(DPPO)­[Pd­(ma)]2} (6) has also been authenticated. X-ray diffraction analysis showed an original situation in which the oxygen atom of the central phosphine oxide moiety bridges the two palladium centers. Addition of trifluoromethanesulfonic acid to DPPO 1 affords the trifunctional phosphine–phosphine oxide–Phosphonium Derivative 7. Upon reaction with [Pd2(dba)3], the palladium hydride κP,O(P),P pincer complex 8 is cleanly formed as the result of P+–H bond activation. Complex 8 is readily deprotonated by DBU (DBU = 1,8-diazabicycloundec-7-ene), and spontaneous oxidative addition of the Ph–P­(O) bond gives the diphosphine–phosphide oxide κP,P(O),P pincer complex 2. Conversely, addition of trifluoromethanesulfonic acid on 2 does not give back the palladium hydride 8 but leads to the diphosphine–hydroxy phosphine κP,P(OH),P pincer complex 9

Derrah E.j. - One of the best experts on this subject based on the ideXlab platform.

  • Chelating assistance of P-C and P-H bond activation at palladium and nickel: Straightforward access to diverse pincer complexes from a diphosphine-phosphine oxide
    'American Chemical Society (ACS)', 2013
    Co-Authors: Derrah E.j., Martin C., Mallet-ladeira Sonia, Miqueu Karinne, Bouhadir G., Bourissou D.
    Abstract:

    cited By 19International audienceThe diphosphine-phosphine oxide (DPPO) [o-i-Pr2P-(C 6H4)]2P(O)Ph (1) reacts with [Ni(cod) 2] (cod = 1,4-cyclooctadiene) to give the diphosphine-phosphide oxide κP,P(O),P pincer complex 3. According to DFT calculations, the Ph-P(O) bond activation involves a three-center P,Cipso,Ni transition state. Reaction of the DPPO ligand 1 with [(nbd)Pd(ma)] (nbd = 2,5-norbornadiene and ma = maleic anhydride) affords the [(DPPO)Pd(ma)] complex 4. Upon heating, the ma coligand is displaced and the κP,P(O),P palladium pincer complex 2 is obtained. The dinuclear complex (DPPO)[Pd(ma)]2 (6) has also been authenticated. X-ray diffraction analysis showed an original situation in which the oxygen atom of the central phosphine oxide moiety bridges the two palladium centers. Addition of trifluoromethanesulfonic acid to DPPO 1 affords the trifunctional phosphine-phosphine oxide-Phosphonium Derivative 7. Upon reaction with [Pd 2(dba)3], the palladium hydride κP,O(P),P pincer complex 8 is cleanly formed as the result of P+-H bond activation. Complex 8 is readily deprotonated by DBU (DBU = 1,8- diazabicycloundec-7-ene), and spontaneous oxidative addition of the Ph-P(O) bond gives the diphosphine-phosphide oxide κP,P(O),P pincer complex 2. Conversely, addition of trifluoromethanesulfonic acid on 2 does not give back the palladium hydride 8 but leads to the diphosphine-hydroxy phosphine κP,P(OH),P pincer complex 9. © 2013 American Chemical Society

Wojciech Grochala - One of the best experts on this subject based on the ideXlab platform.

  • organic Derivatives of mg bh4 2 as precursors towards mgb2 and novel inorganic mixed cation borohydrides
    Dalton Transactions, 2016
    Co-Authors: Wojciech Wegner, Tomasz Jaron, Michal A Dobrowolski, łukasz Dobrzycki, Michal K Cyranski, Wojciech Grochala
    Abstract:

    A series of organic Derivatives of magnesium borohydride, including Mg(BH4)2·1.5DME (DME = 1,2-dimethoxyethane) and Mg(BH4)2·3THF (THF = tetrahydrofuran) solvates and three mixed-cation borohydrides, [Cat]2[Mg(BH4)4], [Cat] = [Me4N], [nBu4N], [Ph4P], have been characterized. The Phosphonium Derivative has been tested as a precursor for synthesis of inorganic mixed-metal borohydrides of magnesium, Mx[Mg(BH4)2+x], M = Li–Cs, via a metathetic method. The synthetic procedure has yielded two new Derivatives of heavier alkali metals M3Mg(BH4)5 (M = Rb, Cs) mixed with amorphous Mg(BH4)2. Thermal decomposition has been studied for both the organic and inorganic magnesium borohydride Derivatives. Amorphous MgB2 has been detected among the products of the thermal decomposition of the solvates studied, together with organic and inorganic impurities.