TY - JOUR
T1 - 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
AU - Allcock, Harry R.
AU - Lavin, Karen D.
AU - Riding, Geoffrey H.
AU - Whittle, Robert R.
AU - Parvez, Masood
PY - 1986/1/1
Y1 - 1986/1/1
N2 - 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.
AB - 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.
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U2 - 10.1021/om00139a019
DO - 10.1021/om00139a019
M3 - Article
AN - SCOPUS:0001461499
VL - 5
SP - 1626
EP - 1635
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 8
ER -