Transsilylation reactions of phosphazene precursors

Wettermark, U. G.; Neilson, Robert H.

doi:10.1021/ic00253a030

Cited by 14 publications

(2 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…N -Silylphosphoranimines of general formula Me 3 SiNP(X)R‘R‘ ‘ have provided access to a variety of new main group element systems, especially phosphazene polymers. Studies in our laboratories have shown that these Si−N−P compounds exhibit at least four modes of reactivity: (1) condensation to polymeric 7 (X = OCH 2 CF 3 or OPh) or cyclic and/or oligomeric (X = halogen) phosphazenes via elimination of Me 3 SiX, (2) substitution at phosphorus, (3) deprotonation−substitution at P -alkyl groups, and (4) Si−N bond cleavage reactions . The utility of N -silylphosphoranimines is enhanced by their straightforward and versatile synthesis .…”

Section: Resultsmentioning

confidence: 99%

Reactions ofN-Silylphosphoranimines with Alcohols: Synthesis and Structure of Cyclotriphosphazenes with Nongeminal Methyl and Phenyl Substituents

Wisian‐Neilson

Johnson²,

Zhang³

et al. 2002

Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

The reactions of Me(3)SiN=P(OR")RR'(R" = Ph, CH(2)CF(3); R, R' = Me, Ph) with alcohols were investigated. With nonequivalent amounts of CF(3)CH(2)OH, the reactions produced high yields of the cyclic phosphazene (Me(2)PN)(3) and both the cis and trans isomers of nongeminally substituted [(Ph)(Me)PN](3). The isomers of this new cyclic phosphazene were separated by column chromatography and characterized by NMR and IR spectroscopy, elemental analysis, and X-ray crystallography. Crystals of the cis isomer 6a have a monoclinic crystal system, while the trans isomer 6b has a triclinic crystal system with two different molecules in an asymmetric unit. The bond lengths and bond angles are very similar to those of the simpler cyclic trimers (Me(2)PN)(3) and (Ph(2)PN)(3.) A likely pathway for the formation of these compounds is discussed.

show abstract

Section: Resultsmentioning

confidence: 99%

Reactions ofN-Silylphosphoranimines with Alcohols: Synthesis and Structure of Cyclotriphosphazenes with Nongeminal Methyl and Phenyl Substituents

Wisian‐Neilson

Johnson²,

Zhang³

et al. 2002

Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…Some related N -phosphorylphosphoranimines have been reported and structurally characterized, , but generally, they do not contain the requisite functional groups on phosphorus. The reactivity of the SiN bond in N -silylphosphoranimines toward nonmetal halides has been utilized to prepare many other SiNP and BNP 8 derivatives. It seemed appropriate, therefore, to investigate the possible synthesis of PNP systems in a similar manner.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Reactivity of SomeN-Phosphorylphosphoranimines

et al. 2002

Self Cite

View full text Add to dashboard Cite

A large series of new N-phosphorylphosphoranimines that bear potentially reactive functional groups on both phosphorus centers were prepared by silicon-nitrogen bond cleavage reactions of N-silylphosphoranimines. Thus, treatment of the N-silylphosphoranimines, Me(3)SiN=P(Me)(R)X (R = Me, Ph; X = OCH(2)CF(3) and R = Me, X = OPh), with phosphoryl chlorides, RP(=O)Cl(2) (R' = Cl, Me, Ph), readily afforded the corresponding N-phosphoryl derivatives, R'P(=O)(Cl)-N=P(Me)(R)X, in high yields. Subsequent reaction with 1 or 2 equiv of the silylamine, Me(3)SiNMe(2), resulted in ligand exchange at the phosphoryl (P=O) group to give the P-dimethylamino analogues, R'P(=O)(NMe(2))N=P(Me)(R)X (R' = Cl, NMe(2), Me, Ph; R = Me, Ph; X = OCH(2)CF(3), OPh). These new N-phosphorylphosphoranimines (and one thiophosphoryl analogue) were obtained as thermally stable, distillable liquids and were characterized by NMR ((1)H, (13)C, and (31)P) spectroscopy and elemental analysis. One member of the series, Cl(2)P(=O)N=P(Me)(Ph)OCH(2)CF(3) (4), was also studied by single-crystal X-ray diffraction which revealed that the formal P(O)-N single bond [1.55(1) A] is shorter than the formal N=PR(2)X double bond [1.60(1) A]. Such structural features are compared to those of similar compounds and discussed in relationship to the unexpected thermolysis pathways observed for these N-phosphorylphosphoranimines, none of which produced poly(phosphazenes).

show abstract

ChemInform Abstract: Transsilylation Reactions of Phosphazene Precursors.

Wettermark

Neilson

1987

ChemInform

View full text Add to dashboard Cite

229ChemInform Abstract The transsilylation reactions of the phosphazene precursor (I) with the chlorosilane (II), the dichlorosilanes (IV) and (VI), and the dichlorodisiloxanes (X) lead to the products (III), and depending on the stoichiometry to (Va) or (Vb), (VIIa) or (VIIb), and (XIa) or (XIb-d), respectively. The chlorosilyl derivatives (Va) and (VIIa) react with PhLi and MeLi to form respectively (IIIa) and the seven-membered ring compound (IX). On treatment with MeLi or BuLi, the chlorosiloxane (XIa) is converted into the alkylsilyl derivatives (XIe). The thermal decomposition reactions of the siloxane-phosphoranimine products (XI) are also studied, but siloxane-phosphazene copolymers are not formed. Instead, poly(dimethylphosphazene) and trifluoroethoxy-terminated siloxanes are obtained.

show abstract

Transsilylation reactions of phosphazene precursors

Cited by 14 publications

References 2 publications

Reactions ofN-Silylphosphoranimines with Alcohols: Synthesis and Structure of Cyclotriphosphazenes with Nongeminal Methyl and Phenyl Substituents

Reactions ofN-Silylphosphoranimines with Alcohols: Synthesis and Structure of Cyclotriphosphazenes with Nongeminal Methyl and Phenyl Substituents

Synthesis, Structure, and Reactivity of SomeN-Phosphorylphosphoranimines

ChemInform Abstract: Transsilylation Reactions of Phosphazene Precursors.

Contact Info

Product

Resources

About