Stabilised phosphazides

Bebbington, M. W. P.; Bourissou, Didier

doi:10.1016/j.ccr.2008.08.009

Cited by 47 publications

(55 citation statements)

References 66 publications

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“…The reaction of 5 with 1‐adamantyl azide (AdN 3 ) is surprisingly clean in several stoichiometric ratios as judged by in situ 1 H and 31 P { 1 H} NMR spectroscopic studies, and the phosphazide complex 9 [L 2 L′ 2 Mg 4 H 4 ] (L′=DipNP(N 3 Ad)Ph 2 ) was obtained in low to moderate crystallised yield (Scheme and Figure ). In this complex, the hydride moieties did not react with the organic azide, as was previously found for a β‐diketiminate‐MgH system, but instead two phosphinoamide ligands were converted to anionic iminophosphorano‐phosphazide ligands (L′ − ) . We have previously found that the phosphinoamide ligand ( L − ) can undergo addition reactions to several unsaturated substrates .…”

Section: Resultsmentioning

confidence: 55%

“…3:P(1)ÀN(1) 1.668(3), P(2)ÀN(2) 1.648(3), P(1)ÀMg(2)2.7971 (15), Mg(1)ÀP(2) 2.6786 (14), Mg(1)ÀN(1) 2.030(3), Mg(2)ÀN(2) 2.044(3),Mg(1)ÀC(49) 2.277(3),Mg(2)ÀC(49) 2.290(3),M g(2)ÀC(51) 2.203(3), C(51)ÀMg(1) ' 2.400(3);N(1)-Mg(1)-P(2) 113.77(9), N(2)-Mg(2)-C(51) 117.89 (12), N(2)-Mg(2)-P(1) 108.61(9),C(51)-Mg(2)-P(1) 121.79 (10), Mg(1)-C(49)-Mg(2)82.07 (10). [8]: 4: P(1)ÀN(1) 1.6621(13), P(2)ÀN(2) 1.6630 (12), P(1)ÀMg(2)' 2.6609(7), P(1)ÀMg(1) 3.0509 (8), Mg(1)ÀP(2) 2.9555(7), P(2)ÀMg(2)2.6841(9), Mg(2)ÀP(1)' 2.6609(7), Mg(1)ÀN(1) 2.0155(13), Mg(1)ÀN(2) 2.0275(13), Mg(1)ÀC(49) 2.2668 (17), Mg(2)ÀC(49) 2.2500 (16), Mg(2)ÀC(50) 2.7718 (19), Mg(1)ÀH(1) 1.96 (2), Mg(2)À H(1) 1.98(2), Mg(2)'ÀH(1) 1.92 (2);N(1)-Mg(1)-N(2) 132.79(5), N(1)-Mg(1)-C(49) 112.74(6), N(2)-Mg(1)-C(49) 111.70(6), N(1)-Mg(1)-H(1)99. 8(6), N(2)-Mg(1)-H(1) 95.8(6), C(49)-Mg(1)-H(1) 89.4(6), P(1)'-Mg(2)-P(2) 110.18 (2), C(49)-Mg(2)-H(1) 89.3(6), P(1)'-Mg(2)-H(1) 133.4(6), P(2)-Mg(2)-H(1) 79.5(6).…”

Section: Synthesisunclassified

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Ring‐Shaped Phosphinoamido‐Magnesium‐Hydride Complexes: Syntheses, Structures, Reactivity, and Catalysis

Fohlmeister

Stasch

2016

Chemistry A European J

117

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A series of magnesium(II) complexes bearing the sterically demanding phosphinoamide ligand, L(-) =Ph2 PNDip(-) , Dip=2,6-diisopropylphenyl, including heteroleptic magnesium alkyl and hydride complexes are described. The ligand geometry enforces various novel ring and cluster geometries for the heteroleptic compounds. We have studied the stoichiometric reactivity of [(LMgH)4 ] towards unsaturated substrates, and investigated catalytic hydroborations and hydrosilylations of ketones and pyridines. We found that hydroborations of two ketones with pinacolborane using various Mg precatalysts is very rapid at room temperature with very low catalyst loadings, and ketone hydrosilylation using phenylsilane is rapid at 70 °C. Our studies point to an insertion/σ-bond metathesis catalytic cycle of an in situ formed "MgH2 " active species.

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Section: Resultsmentioning

confidence: 55%

Section: Synthesisunclassified

Ring‐Shaped Phosphinoamido‐Magnesium‐Hydride Complexes: Syntheses, Structures, Reactivity, and Catalysis

Fohlmeister

Stasch

2016

Chemistry A European J

117

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“…The formation of the phosphazide14 complexes [( Dip L)( DipN2 L)Li 2 ] 7 and [( DipN2 L) 2 Li 2 ] 8 can be explained by an incomplete N 2 elimination in the Staudinger reaction leading to 3 (see Scheme ). Gas evolution in the synthesis of 3 (and 4 ) is already evident at very low temperatures, but very minor impurities can be found in some preparations of 3 , as judged by 31 P{ 1 H} NMR spectroscopy, which caused the formation of [( Dip L)( DipN2 L)Li 2 ] 7 and [( DipN2 L) 2 Li 2 ] 8 .…”

Section: Resultsmentioning

confidence: 99%

Structural Diversity in Sterically Demanding Diiminophosphinato Alkali Metal Complexes

Hawley

Stasch

2014

Eur J Inorg Chem

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We have prepared the new aminophosphine Ph2PNHMes 2 [Mes = mesityl (2,4,6‐Me3C6H2)], and the aminoiminophosphorane Ph2P(=NMes)NHMes 4 (MesLH), and obtained the new alkali metal complexes [(DipLLi)2] 5 [DipL = Ph2P(NDip)2, Dip = 2,6‐iPr2C6H3], [(MesLLi)2] 6, [(DipL)(DipN2L)Li2] 7 [DipN2L = Ph2P(NDip)(N3Dip)], [(DipN2L)2Li2] 8, [DipLLi(THF)] 9, [DipLLi(THF)2] 10, [(DipLNa)2] 11, [(MesLNa)n] 12, [DipLNa(THF)2] 13, [{MesLNa(THF)}2] 14 and [MesLK] 16 by deprotonation of their respective ligand precursors with standard strong alkali metal bases in various solvents. The crystal structures of 2, 4–6, 7·8, 9–14, and 16 are reported. The different coordination modes in their solid‐state structures are discussed and generally compared to the solution behavior of those species.

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“…Recently, stable phosphazides were obtained in connection with the synthesis of Schwesinger P 1 ‐bases through a Staudinger reaction 20. The field of stable phosphazides was extensively reviewed by Bebbington and Bourissou in 2009 21…”

Section: Introductionmentioning

confidence: 99%

Constrained‐Geometry Bisphosphazides Derived from 1,8‐Diazidonaphthalene: Synthesis, Spectroscopic Characteristics, Structural Features, and Theoretical Investigations

Kögel

Abacilar

Weber

et al. 2014

Chemistry A European J

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Investigations on the Staudinger reaction between 1,8-diazidonaphthalene and phosphorous(III) building blocks, a key step in the synthesis of superbasic bisphosphazene proton sponges, yielded a set of bisphosphazides with a constrained geometry 1,8-disubstituted naphthalene backbone. This compound class has attracted our interest not only due to their surprisingly high stability, but in particular because of their theoretically predicted basicity in the range of their bisphosphazene analogues that can be referred to the constrained geometry interaction of two highly basic nitrogen atoms. Eleven new bisphosphazides bearing simple P-amino groups as well as P-guanidino substituents, azaphosphatrane moieties, P2 building blocks, or chiral P-amino substituents derived from L-proline are presented. They were studied concerning their spectroscopic properties and partly also their chromophoric and structural features. In the case of the pyrrolidino-substituted TPPN(2N2) (TPPN = 1,8-bis(trispyrrolidinophosphazenyl)naphthalene), the stepwise nitrogen elimination is investigated theoretically and experimentally, which led to the isolation and structural characterization of TPPN(1N2) bearing a phosphazide and a phosphazene functionality in one molecule. Attempts to protonate the obtained bisphosphazides and to prove the computationally predicted pKBH(+) values through NMR titration reactions resulted in their decay, which again was rationalized by theoretical calculations. Altogether we present the so far most extensive spectroscopic, structural and theoretical investigation of constrained geometry bisphosphazides and their Brønsted and Lewis basic properties.

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Stabilised phosphazides

Cited by 47 publications

References 66 publications

Ring‐Shaped Phosphinoamido‐Magnesium‐Hydride Complexes: Syntheses, Structures, Reactivity, and Catalysis

Ring‐Shaped Phosphinoamido‐Magnesium‐Hydride Complexes: Syntheses, Structures, Reactivity, and Catalysis

Structural Diversity in Sterically Demanding Diiminophosphinato Alkali Metal Complexes

Constrained‐Geometry Bisphosphazides Derived from 1,8‐Diazidonaphthalene: Synthesis, Spectroscopic Characteristics, Structural Features, and Theoretical Investigations

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