Reactions of Ferrocenyl- and Ruthenocenylphosphazenes with Lithiometallocenes and the X-ray Structures of N3P3F4(η-C5H4)2Fe, [N3P3F3{(η-C5H4)2Fe}{(η-C5H4)Fe(η-C5H5)}], 1,5-N4P4F6(η-C5H4)2Fe, and 1,5,3,7-N4P4F4[(η-C5H4)2RU]21

Harry R. Allcock, Karen D. Lavin, Geoffrey H. Riding, Robert R. Whittle, Masood Parvez

Research output: Contribution to journalArticlepeer-review

34 Scopus citations

Abstract

Cyclotri- and cyclotetraphosphazenes that bear fluoro and ferrocenyl or ruthenocenyl side groups undergo fluorine replacement with mono- or dilithioferrocene or mono- or dilithioruthenocene or with methyllithium or phenyllithium. The pattern of fluorine replacement is complex and depends on coordination of the incoming organolithium reagent with the skeletal nitrogen atoms and on steric hindrance factors. An unusual “double-transannular” ruthenocenylphosphazene was isolated from the cyclotetraphosphazene system. Four metallocenylphosphazenes have been studied by X-ray crystallography. Crystals of N3P3F4(η-C5H4)2Fe (1a) are triclinic, space group PI, with a = 8.074 (1) Å, b = 8.164 (1) Å, c = 11.521 (2) Å, a = 91.37 (2)°, β = 92.31 (2)°, γ = 118.2 (1)°, V = 667.9 Å3, and Z = 2. The structure was refined to discrepancy indices R = 0.038 and Rw= 0.051. The phosphazene ring is severely distorted in response to the presence of the transannular ferrocenyl unit. cis-non-gem-[N3P3F3{(η-C5H4)2Fe}{(η-C5H4)Fe(η-C5H5)}] (7) gives orthorhombic crystals, space group P212121, with a = 10.398 (2) Å, b = 10.644 (2) Å, c = 18.769 (2) Å, V = 2077.3 Å3, and Z = 4. The structure was refined to discrepancy indices R = 0.042 and Rw= 0.059. The phosphazene ring is highly distorted in this molecule. The ferrocene transannular tetramer 1,5-N4P4F6(η-C5H4)2Fe (3a) gives monoclinic crystals, space group P21/n, with a = 8.668 (1) Å, b = 12.823 (1) Å, c = 14.560 (2) Å, β = 100.86 (1)°, V = 1589.3 Å3, and Z = 4. The structure was refined to discrepancy indices R = 0.032 and Rw= 0.041. Even more distortion of the phosphazene ring is found in this molecule. Crystals of the double-transannular phosphazene tetramer 1,5,3,7-N4P4F4{(η-C5H4)2Ru}2 (10) are monoclinic, space group P2ltwith a = 7.719 (1) Å, b = 12.151 (5) Å, c = 15.606 (2) Å, β = 101.93 (1)°, V = 1432.1 Å3, and Z = 2. The eight-membered cyclotetraphosphazene ring is severely puckered to adapt to the constraints imposed by the two ruthenocene systems.

Original languageEnglish (US)
Pages (from-to)1626-1635
Number of pages10
JournalOrganometallics
Volume5
Issue number8
DOIs
StatePublished - Jan 1 1986

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Fingerprint Dive into the research topics of 'Reactions of Ferrocenyl- and Ruthenocenylphosphazenes with Lithiometallocenes and the X-ray Structures of N<sub>3</sub>P3F<sub>4</sub>(η-C<sub>5</sub>H<sub>4</sub>)<sub>2</sub>Fe, [N<sub>3</sub>P<sub>3</sub>F<sub>3</sub>{(η-C<sub>5</sub>H<sub>4</sub>)<sub>2</sub>Fe}{(η-C<sub>5</sub>H<sub>4</sub>)Fe(η-C<sub>5</sub>H<sub>5</sub>)}], 1,5-N<sub>4</sub>P<sub>4</sub>F<sub>6</sub>(η-C<sub>5</sub>H<sub>4</sub>)<sub>2</sub>Fe, and 1,5,3,7-N<sub>4</sub>P<sub>4</sub>F<sub>4</sub>[(η-C<sub>5</sub>H<sub>4</sub>)<sub>2</sub>RU]<sub>2</sub><sup>1</sup>'. Together they form a unique fingerprint.

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