Abstract
Abstract The synthesis of novel bis(N-aryl-imino-phosphoranyl)methanes of the type CH2(PR2˭N-Ar)2 has been accomplished by reaction of methylene-bisphosphines with arylazides. These compounds have been fully characterized by 1H, 31P and 13C NMR, IR spectroscopy, Field Desorption Mass Spectroscopy (˭ FDMS) and elemental analysis. Variable temperature NMR experiments and single crystal X-ray structure determinations of CH2(PPh2˭N-C6H4-CH3-4)2 (la) and CH2(PMe2˭N-C6H4-NO2-4)2 (1f) reveal that bis(N-aryl-imino-phosphorany1)methane occurs as tautomer 1. Crystals of la are orthorhombic, space group Pcab, with a = 26.602(2), b = 20.521(1), c = 11.8859(7) A and V = 6488.5(7) A3 (2 = 8, R = 0.045 and Rw = 0.066). The crystals of lf are monoclinic, space group C/2c, with a = 20.153(4), b = 5.952(1), c = 16.930(5) A, β = 106.24(3)° and V = 1949.6(6) A3 (Z = 4, molecular symmetry C2, Rw = 0.051 and R, = 0.079). Both molecules consist of 2 iminophosphoranyl units bridged by a methylene group. The P˭N bond distances of...
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