Chemistry of Boratophosphazenes: Synthesis of Borazine-Phosphazene Hybrid Cations, and New Inorganic Heterocycles by Skeletal Substitution Reactions

Gates, Derek P.; McWilliams, Andrew R.; Ziembinski, Ralf; Liable‐Sands, Louise M.; Guzei, Ilia A.; Yap, Glenn P. A.; Rheingold, Arnold L.; Manners, Ian

doi:10.1002/(sici)1521-3765(19980807)4:8<1489::aid-chem1489>3.0.co;2-q

Cited by 29 publications

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“…Among the family of compounds that have been investigated for this purpose include cyclophosphazenes, 1-4 cyclosiloxanes, [5][6][7][8][9] borazines, [10][11][12][13] Al-N rings [14][15] and Al-C rings. [16][17] The main strategy in this game plan is to build a central 'inorganic core' which contains several reactive sites.…”

Section: Introductionsupporting

confidence: 79%

Multi-functional architectures supported on organostannoxane scaffolds

et al. 2008

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Section: Introductionsupporting

confidence: 79%

Multi-functional architectures supported on organostannoxane scaffolds

et al. 2008

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“…The central N 3 P 2 B ring in 9 slightly deviates from planarity. The B−Cl bond length (1.782(2) Å) in the cationic part of 9 is shorter than the B−Cl distances in its counteranion (average 1.878 Å) and comparable to that reported in the β‐diketiminate‐derived borenium ion (1.740(3) Å) ,. The B−N bond lengths in 9 (1.462(1) and 1.453(1) Å) are slightly shorter than that in its precursor LBH 2 (1.588(5) and 1.615(5) Å) .…”

Section: Resultsmentioning

confidence: 53%

Fine‐Tuning of Lewis Acidity: The Case of Borenium Hydride Complexes Derived from Bis(phosphinimino)amide Boron Precursors

Jaiswal

Prashanth

Singh

2016

Chemistry A European J

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Reactions of bis(phosphinimino)amines LH and L'H with Me2 S⋅BH2 Cl afforded chloroborane complexes LBHCl (1) and L'BHCl (2), and the reaction of L'H with BH3 ⋅Me2 S gave a dihydridoborane complex L'BH2 (3) (LH=[{(2,4,6-Me3 C6 H2 N)P(Ph2 )}2 N]H and L'H=[{(2,6-iPr2 C6 H3 N)P(Ph2 )}2 N]H). Furthermore, abstraction of a hydride ion from L'BH2 (3) and LBH2 (4) mediated by Lewis acid B(C6 F5 )3 or the weakly coordinating ion pair [Ph3 C][B(C6 F5 )4 ] smoothly yielded a series of borenium hydride cations: [L'BH](+) [HB(C6 F5 )3 ](-) (5), [L'BH](+) [B(C6 F5 )4 ](-) (6), [LBH](+) [HB(C6 F5 )3 ](-) (7), and [LBH](+) [B(C6 F5 )4 ](-) (8). Synthesis of a chloroborenium species [LBCl](+) [BCl4 ](-) (9) without involvement of a weakly coordinating anion was also demonstrated from a reaction of LBH2 (4) with three equivalents of BCl3 . It is clear from this study that the sterically bulky strong donor bis(phosphinimino)amide ligand plays a crucial role in facilitating the synthesis and stabilization of these three-coordinated cationic species of boron. Therefore, the present synthetic approach is not dependent on the requirement of weakly coordinating anions; even simple BCl4 (-) can act as a counteranion with borenium cations. The high Lewis acidity of the boron atom in complex 8 enables the formation of an adduct with 4-dimethylaminopyridine (DMAP), [LBH⋅(DMAP)](+) [B(C6 F5 )4 ](-) (10). The solid-state structures of complexes 1, 5, and 9 were investigated by means of single-crystal X-ray structural analysis.

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“…In addition, [Cl 3 P N PCl 3 ][PCl 6 ] is proposed as an intermediate in the formation of poly(dichlorophosphazene) via the living cationic polymerization of Cl 3 P NSiMe 3 with PCl 5 (Honeyman et al, 1995). As part of our studies on the chemistry of boroncontaining heterophosphazene ring systems (Gates et al, 1998;McWilliams et al, 2002), we discovered that the tetrachloroborate salt [Cl 3 P N PCl 3 ][BCl 4 ] reacted quickly with early transition metal halides in chlorinated solvents to produce BCl 3 gas and a series of new bis(trichlorophosphine)iminium salts with transition-metal-containing counter-ions, namely the title compounds (I)±(IV) (Figs. 1±4).…”

Section: Commentmentioning

confidence: 99%

Bis(trichlorophosphine)iminium salts, [Cl₃P=N=PCl₃]⁺, with transition metal halide counter-ions

et al. 2002

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The structures of four bis(trichlorophosphine)iminium [[Cl(3)P=N=PCl(3)](+); systematic name: trichloro[(trichlorophosphoranylidene)iminio]phosphorus(V)] salts, namely bis(trichlorophosphine)iminium hexachloroniobate, (Cl(6)NP(2))[NbCl(6)], (I), bis(trichlorophosphine)iminium hexachlorotantalate, (Cl(6)NP(2))[TaCl(6)], (II), bis(trichlorophosphine)iminium tri-micro-chloro-bis[trichlorotitanium(IV)], (Cl(6)NP(2))[Ti(2)Cl(9)], (III), and bis[bis(trichlorophosphine)iminium] di-micro-chloro-bis[tetrachlorozirconium(IV)], (Cl(6)NP(2))(2)[Zr(2)Cl(10)], (IV), have been determined. The P=N distances in the discrete [Cl(3)P=N=PCl(3)](+) moieties in structures (I), (II) and (IV) range from 1.5460 (14) to 1.5554 (16) A, and the P=N=P angles range from 136.8 (3) to 143.4 (4) degrees. The [Cl(3)P=N=PCl(3)](+) cation in (III) is disordered and the calculated geometries for the cation are therefore less reliable. Compounds (I) and (II) are isostructural and the metal anions have slightly distorted octahedral geometries. The anion in compound (III) consists of two distorted octahedral Ti centres linked by three micro (2)-Cl atoms, while in compound (IV), the dianion is derived from two distorted edge-shared ZrCl(6) octahedra.

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Chemistry of Boratophosphazenes: Synthesis of Borazine-Phosphazene Hybrid Cations, and New Inorganic Heterocycles by Skeletal Substitution Reactions

Abstract: The structural characterization of the boratophosphazene N-(PCl 2 NMe) 2 BCl 2 (1) is reported and reveals a distorted structure in which the boron atom is bent out of the plane of the other ring atoms (0.39 (1) show the presence of planar rings with B ± N bond lengths (ca.

Cited by 29 publications

References 29 publications

Multi-functional architectures supported on organostannoxane scaffolds

Multi-functional architectures supported on organostannoxane scaffolds

Fine‐Tuning of Lewis Acidity: The Case of Borenium Hydride Complexes Derived from Bis(phosphinimino)amide Boron Precursors

Bis(trichlorophosphine)iminium salts, [Cl₃P=N=PCl₃]⁺, with transition metal halide counter-ions

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Chemistry of Boratophosphazenes: Synthesis of Borazine-Phosphazene Hybrid Cations, and New Inorganic Heterocycles by Skeletal Substitution Reactions

Abstract: The structural characterization of the boratophosphazene N-(PCl 2 NMe) 2 BCl 2 (1) is reported and reveals a distorted structure in which the boron atom is bent out of the plane of the other ring atoms (0.39 (1) show the presence of planar rings with B ± N bond lengths (ca.

Cited by 29 publications

References 29 publications

Multi-functional architectures supported on organostannoxane scaffolds

Multi-functional architectures supported on organostannoxane scaffolds

Fine‐Tuning of Lewis Acidity: The Case of Borenium Hydride Complexes Derived from Bis(phosphinimino)amide Boron Precursors

Bis(trichlorophosphine)iminium salts, [Cl3P=N=PCl3]+, with transition metal halide counter-ions

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Bis(trichlorophosphine)iminium salts, [Cl₃P=N=PCl₃]⁺, with transition metal halide counter-ions