Reactivity of a Cyclothiaphosphazene towards Grignard Reagents. Crystal Structure of the 1:1 Adduct of the Bi(cyclothiaphosphazene)2 and Benzene

DOI: 10.1039/DT9900001613

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1613 - 1619 (1990)

Update date:2022-08-02

Topics:

Authors:

Herrema, Jan K.

Jekel, Andries P.

Winter, Herman

Grampel, Johan C. van de

Meetsma, Auke

et al. et al.

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Article abstract of DOI:10.1039/DT9900001613

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 MgBu^tCl 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 <2.211 6(9) Angstroem> 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.