- Reactivity of a Cyclothiaphosphazene towards Grignard Reagents. Crystal Structure of the 1:1 Adduct of the Bi(cyclothiaphosphazene)2 and Benzene
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Reactions of the ring system trans-NPCl2(NSOPh)2 (1) with MgMeCl and an excess of propan-2-ol in tetrahydrofuran show that chlorine substitution occurs both along a nucleophilic substitution pattern and a metal-halogen exchange process, the latter giving rise to the formation of bicyclic compounds.For reactions of this ring system with MgButCl or the organosilyl Grignard reagents Mg(CH2SiMe3)Cl and MgCl nucleophilic substitution appears to be the preferential process.Application of the copper-assisted Grignard reagents MgRCl-n3)>4> (R = alkyl) and alkyl iodides, allyl bromide, or propan-2-ol leads to the formation of dialkyl, alkylallyl, or alkylhydrido derivatives, according to an initial metal-halogen exchange process.The crystal and molecular structure of the bicyclic compound 2*C6H6 has been determined.Crystals are triclinic, space group P1, a = 8.063(1), b = 8.979(1), c = 12.712(3) Angstroem, α = 71.38(1), β = 74.13(1), γ = 86.57(1) deg, and Z = 1.The basic structure consists of two six-membered N3PS2 rings coupled by a P-P bond with the methyl groups in trans position.Mean bond lengths are N-P 1.614(2), N-S 1.565(5), 1.585(1), S-O 1.436(1), S-C 1.768(1), and C-C (phenyl) 1.388(1) Angstroem.The endocyclic angles at P and S are 114.6(1) and 113.3(4) deg (average), respectively, and those at N range from 121.3(1) to 124.8(1) deg.
- Herrema, Jan K.,Jekel, Andries P.,Winter, Herman,Grampel, Johan C. van de,Meetsma, Auke,et al.
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p. 1613 - 1619
(2007/10/02)
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