Synthesis and Structure of Metallocene Cyclophosphazene Derivatives

Harry R. Allcock, Karen D. Lavin, Geoffrey H. Riding, Paul R. Suszko, Robert R. Whittle

Research output: Contribution to journalArticle

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Abstract

Significant mechanistic differences exist between the reactions of mono- and dilithioferrocene or ruthenocene with P-F or P-Cl bonds in cyclophosphazenes. The fluorophosphazenes (NPF2)3 and (NPF2)4 react by a nucleophilic-type substitution pathway to yield mono and bis nongeminal metallocenyl derivatives (6–9) or transannular bridged metallocenylphosphazenes (10–13). By contrast, the chlorophosphazene (NPCl2)3 reacts initially by a metal-halogen exchange pathway to generate an unusual series of metallocenyl cyclophosphazenes and -bi(cyclophosphazenes) (18–20), including examples in which chloro metallocene units are linked to phosphorus (21,22) and one in which a ferrocene unit bridges the P-P linkage site connecting two cyclophosphazene rings (23). Cleavage of the phosphazene skeleton occurs with (NPCl2)4. The molecular structures of four ferrocenyl- and ruthenocenylcyclophosphazenes prepared by these routes have been determined by X-ray diffraction techniques. Confirmation of a covalent linkage between a cyclopentadienyl group and the phosphazene ring was obtained for the prototype, N3P3F5(η-C5H4)Fe(η-C5H4) (6a). The effect of transannular bridging of the phosphazene ring by metallocene units was studied in N3P3F4(η-C5H4)2Ru (10b) and N4P4F6(η-C5H4)2Ru (12b). The structure of species N6P6Cl8(η-C5H4)2Fe (23), with two phosphazene rings linked by a P-P bond and a ferrocenyl bridging site, was also examined. The structural peculiarities are a consequence of the low deformability of the metallocenyl units and the relatively high flexibility of the phosphazene rings. Crystal data: Crystals of 6a are monoclinic with the space group C2/c, a = 19.946 (9) Å, b = 6.922 (2) Å, c = 22.340 (9) Å, β = H 1-19 (5)°, and V = 2876 (4) Å3 and Z = 8. Crystals of 10b are triclinic with the space group C2/c, a = 19.946 (9) Å, b = 6.92 (2) Å, c = 22.340 (9) Å, #x03B2; = 111.19 (5)°, and V = 2876 (4) Å3 and Z = 8. Crystals of 10b are triclinic with the space group PI and with a = 8.029 (2) Å, b = 8.286 (4) Å, c = 11.555 (7) Å, and α = 87.16 (4)°, β = 87.91 (3)°, γ = 61.83 (3)°, and V = 676.7 (7) Å3 and Z = 2. Crystals of 12b are orthorhombic with the space group Pbca and with a = 15.534 (3) Å, b = 14.610 (3) Å, c = 14.430 (2) Å, and V = 3275 (2) Å3 and Z = 8. Crystals of 23 are monoclinic with the space group P21/4 and with a = 11.064 (2) Å, b = 13.019 (4) Å, c = 18.196 (3) Å, β = 102.55 (3)°, and V = 2558 (2) Å3 and Z = 4.

Original languageEnglish (US)
Pages (from-to)2337-2347
Number of pages11
JournalJournal of the American Chemical Society
Volume106
Issue number8
DOIs
StatePublished - Jan 1 1984

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Derivatives
Crystals
Halogens
Molecular Structure
Skeleton
X-Ray Diffraction
Phosphorus
Metals
Formability
Molecular structure
metallocene
Substitution reactions
X ray diffraction
ferrocene
ruthenocene

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Allcock, Harry R. ; Lavin, Karen D. ; Riding, Geoffrey H. ; Suszko, Paul R. ; Whittle, Robert R. / Synthesis and Structure of Metallocene Cyclophosphazene Derivatives. In: Journal of the American Chemical Society. 1984 ; Vol. 106, No. 8. pp. 2337-2347.
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title = "Synthesis and Structure of Metallocene Cyclophosphazene Derivatives",
abstract = "Significant mechanistic differences exist between the reactions of mono- and dilithioferrocene or ruthenocene with P-F or P-Cl bonds in cyclophosphazenes. The fluorophosphazenes (NPF2)3 and (NPF2)4 react by a nucleophilic-type substitution pathway to yield mono and bis nongeminal metallocenyl derivatives (6–9) or transannular bridged metallocenylphosphazenes (10–13). By contrast, the chlorophosphazene (NPCl2)3 reacts initially by a metal-halogen exchange pathway to generate an unusual series of metallocenyl cyclophosphazenes and -bi(cyclophosphazenes) (18–20), including examples in which chloro metallocene units are linked to phosphorus (21,22) and one in which a ferrocene unit bridges the P-P linkage site connecting two cyclophosphazene rings (23). Cleavage of the phosphazene skeleton occurs with (NPCl2)4. The molecular structures of four ferrocenyl- and ruthenocenylcyclophosphazenes prepared by these routes have been determined by X-ray diffraction techniques. Confirmation of a covalent linkage between a cyclopentadienyl group and the phosphazene ring was obtained for the prototype, N3P3F5(η-C5H4)Fe(η-C5H4) (6a). The effect of transannular bridging of the phosphazene ring by metallocene units was studied in N3P3F4(η-C5H4)2Ru (10b) and N4P4F6(η-C5H4)2Ru (12b). The structure of species N6P6Cl8(η-C5H4)2Fe (23), with two phosphazene rings linked by a P-P bond and a ferrocenyl bridging site, was also examined. The structural peculiarities are a consequence of the low deformability of the metallocenyl units and the relatively high flexibility of the phosphazene rings. Crystal data: Crystals of 6a are monoclinic with the space group C2/c, a = 19.946 (9) {\AA}, b = 6.922 (2) {\AA}, c = 22.340 (9) {\AA}, β = H 1-19 (5)°, and V = 2876 (4) {\AA}3 and Z = 8. Crystals of 10b are triclinic with the space group C2/c, a = 19.946 (9) {\AA}, b = 6.92 (2) {\AA}, c = 22.340 (9) {\AA}, #x03B2; = 111.19 (5)°, and V = 2876 (4) {\AA}3 and Z = 8. Crystals of 10b are triclinic with the space group PI and with a = 8.029 (2) {\AA}, b = 8.286 (4) {\AA}, c = 11.555 (7) {\AA}, and α = 87.16 (4)°, β = 87.91 (3)°, γ = 61.83 (3)°, and V = 676.7 (7) {\AA}3 and Z = 2. Crystals of 12b are orthorhombic with the space group Pbca and with a = 15.534 (3) {\AA}, b = 14.610 (3) {\AA}, c = 14.430 (2) {\AA}, and V = 3275 (2) {\AA}3 and Z = 8. Crystals of 23 are monoclinic with the space group P21/4 and with a = 11.064 (2) {\AA}, b = 13.019 (4) {\AA}, c = 18.196 (3) {\AA}, β = 102.55 (3)°, and V = 2558 (2) {\AA}3 and Z = 4.",
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Synthesis and Structure of Metallocene Cyclophosphazene Derivatives. / Allcock, Harry R.; Lavin, Karen D.; Riding, Geoffrey H.; Suszko, Paul R.; Whittle, Robert R.

In: Journal of the American Chemical Society, Vol. 106, No. 8, 01.01.1984, p. 2337-2347.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Synthesis and Structure of Metallocene Cyclophosphazene Derivatives

AU - Allcock, Harry R.

AU - Lavin, Karen D.

AU - Riding, Geoffrey H.

AU - Suszko, Paul R.

AU - Whittle, Robert R.

PY - 1984/1/1

Y1 - 1984/1/1

N2 - Significant mechanistic differences exist between the reactions of mono- and dilithioferrocene or ruthenocene with P-F or P-Cl bonds in cyclophosphazenes. The fluorophosphazenes (NPF2)3 and (NPF2)4 react by a nucleophilic-type substitution pathway to yield mono and bis nongeminal metallocenyl derivatives (6–9) or transannular bridged metallocenylphosphazenes (10–13). By contrast, the chlorophosphazene (NPCl2)3 reacts initially by a metal-halogen exchange pathway to generate an unusual series of metallocenyl cyclophosphazenes and -bi(cyclophosphazenes) (18–20), including examples in which chloro metallocene units are linked to phosphorus (21,22) and one in which a ferrocene unit bridges the P-P linkage site connecting two cyclophosphazene rings (23). Cleavage of the phosphazene skeleton occurs with (NPCl2)4. The molecular structures of four ferrocenyl- and ruthenocenylcyclophosphazenes prepared by these routes have been determined by X-ray diffraction techniques. Confirmation of a covalent linkage between a cyclopentadienyl group and the phosphazene ring was obtained for the prototype, N3P3F5(η-C5H4)Fe(η-C5H4) (6a). The effect of transannular bridging of the phosphazene ring by metallocene units was studied in N3P3F4(η-C5H4)2Ru (10b) and N4P4F6(η-C5H4)2Ru (12b). The structure of species N6P6Cl8(η-C5H4)2Fe (23), with two phosphazene rings linked by a P-P bond and a ferrocenyl bridging site, was also examined. The structural peculiarities are a consequence of the low deformability of the metallocenyl units and the relatively high flexibility of the phosphazene rings. Crystal data: Crystals of 6a are monoclinic with the space group C2/c, a = 19.946 (9) Å, b = 6.922 (2) Å, c = 22.340 (9) Å, β = H 1-19 (5)°, and V = 2876 (4) Å3 and Z = 8. Crystals of 10b are triclinic with the space group C2/c, a = 19.946 (9) Å, b = 6.92 (2) Å, c = 22.340 (9) Å, #x03B2; = 111.19 (5)°, and V = 2876 (4) Å3 and Z = 8. Crystals of 10b are triclinic with the space group PI and with a = 8.029 (2) Å, b = 8.286 (4) Å, c = 11.555 (7) Å, and α = 87.16 (4)°, β = 87.91 (3)°, γ = 61.83 (3)°, and V = 676.7 (7) Å3 and Z = 2. Crystals of 12b are orthorhombic with the space group Pbca and with a = 15.534 (3) Å, b = 14.610 (3) Å, c = 14.430 (2) Å, and V = 3275 (2) Å3 and Z = 8. Crystals of 23 are monoclinic with the space group P21/4 and with a = 11.064 (2) Å, b = 13.019 (4) Å, c = 18.196 (3) Å, β = 102.55 (3)°, and V = 2558 (2) Å3 and Z = 4.

AB - Significant mechanistic differences exist between the reactions of mono- and dilithioferrocene or ruthenocene with P-F or P-Cl bonds in cyclophosphazenes. The fluorophosphazenes (NPF2)3 and (NPF2)4 react by a nucleophilic-type substitution pathway to yield mono and bis nongeminal metallocenyl derivatives (6–9) or transannular bridged metallocenylphosphazenes (10–13). By contrast, the chlorophosphazene (NPCl2)3 reacts initially by a metal-halogen exchange pathway to generate an unusual series of metallocenyl cyclophosphazenes and -bi(cyclophosphazenes) (18–20), including examples in which chloro metallocene units are linked to phosphorus (21,22) and one in which a ferrocene unit bridges the P-P linkage site connecting two cyclophosphazene rings (23). Cleavage of the phosphazene skeleton occurs with (NPCl2)4. The molecular structures of four ferrocenyl- and ruthenocenylcyclophosphazenes prepared by these routes have been determined by X-ray diffraction techniques. Confirmation of a covalent linkage between a cyclopentadienyl group and the phosphazene ring was obtained for the prototype, N3P3F5(η-C5H4)Fe(η-C5H4) (6a). The effect of transannular bridging of the phosphazene ring by metallocene units was studied in N3P3F4(η-C5H4)2Ru (10b) and N4P4F6(η-C5H4)2Ru (12b). The structure of species N6P6Cl8(η-C5H4)2Fe (23), with two phosphazene rings linked by a P-P bond and a ferrocenyl bridging site, was also examined. The structural peculiarities are a consequence of the low deformability of the metallocenyl units and the relatively high flexibility of the phosphazene rings. Crystal data: Crystals of 6a are monoclinic with the space group C2/c, a = 19.946 (9) Å, b = 6.922 (2) Å, c = 22.340 (9) Å, β = H 1-19 (5)°, and V = 2876 (4) Å3 and Z = 8. Crystals of 10b are triclinic with the space group C2/c, a = 19.946 (9) Å, b = 6.92 (2) Å, c = 22.340 (9) Å, #x03B2; = 111.19 (5)°, and V = 2876 (4) Å3 and Z = 8. Crystals of 10b are triclinic with the space group PI and with a = 8.029 (2) Å, b = 8.286 (4) Å, c = 11.555 (7) Å, and α = 87.16 (4)°, β = 87.91 (3)°, γ = 61.83 (3)°, and V = 676.7 (7) Å3 and Z = 2. Crystals of 12b are orthorhombic with the space group Pbca and with a = 15.534 (3) Å, b = 14.610 (3) Å, c = 14.430 (2) Å, and V = 3275 (2) Å3 and Z = 8. Crystals of 23 are monoclinic with the space group P21/4 and with a = 11.064 (2) Å, b = 13.019 (4) Å, c = 18.196 (3) Å, β = 102.55 (3)°, and V = 2558 (2) Å3 and Z = 4.

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