Chalcogenation reactions of a stable ferrocenyldiphosphene: Formation of thia‐, selena‐, and telluradiphosphiranes

Abstract

The reactions of TbtP PTbt (Tbt = 2,4,

Planar P6E6 (E = Se, S) macrocycles incorporating P2N2 scaffolds

“…1-3 Although several organophosphorus(III)-tellurium heterocycles of the type cyclo-(RP) x Te y (x>y) have been prepared, characterization has been limited to 31 P and 125 Te NMR spectra or mass spectrometric data. [4][5][6][7][8][9] We and others have shown that terminal P-Te bonds are stabilized by an anionic charge 10,11 and that property is manifested in the recent report of the synthesis and NMR characterization of the first binary P-Te anion [P 4 Te 2 ] 2− . 12 In our studies of the oxidation of the acyclic monoanions [TePR 2 NPR 2 Te] − (1, R = i Pr, t Bu) we found that one-electron oxidation with I 2 results in formation of ditellurides, which may adopt either acyclic or spirocyclic structures; [13,14] twoelectron oxidation generates the cyclic cation [N(P i Pr 2 Te) 2 ] + (2), which incorporates a five-membered NP(V) 2 Te 2 ring.…”

“…1.566 (7), P-N bridging (range) 1.697(7)-1.719 (7); P1-Te1-Na2 80.41 (8), P2-Te2-Na2 80.35 (8), Te1-Na2-Te2 125.1 (1), N3-Na1-N4 101.2(2), N5-Na1-N6 72.6(3), N7-Na2-N8 76.5(3). 2.350(8), Na1-N8 2.351(8), Na1-N1 2.802 (7), Na1-N6 2.848 (7), Na1-P2 3.172(4), Na1-P4 3.208(4), Na2-N7 2.347 (7), Na2-N4 2.349 (7), Na2-N2 2.767 (7), Na2-N6 2.860(8), Na2-P2 3.167(4), Na2-P3 3.204(4), Na3-N3 2.303(8), Na3-N7 2.310 (7), Na3-N5 2.886(8), Na3-N2 2.962 (7), Na3-P3 3.194(4), Na3-P1 3.240(4), Na4-N8 2.312(8), Na4-N3 2.336(8), Na4-N5 2.833(8), Na4-N1 2.960(8), Na4-P4 3.167(4), Na4-P1 3.224(5), Na5-N16 2.316(8), Na5-N11 2.328 (7), Na5-N14 2.848(8), Na5-N9 2.863(7), Na5-P7 3.154(4), Na5-P6 3.174(4), Na6-N16 2.337(8), Na6-N12 2.343 (7), Na6-N9 2.903 (7), Na6-N13 3.018(7), Na6-P5 3.217(4), Na6-P7 3.295(4), Na7-N15 2.335 (7), Na7-N12 2.344 (7), Na7-N10 2.762 (7), Na7-N13 2.807 (7), Na7-P5 3.166(4), Na7-P8 3.167(4), Na8-N11 2.317 (7), Na8-N15 2.326(8), Na8-N14 2.914 (7), Na8-N10 3.044 (7), Na8-P8 3.215(4), Na8-P6 3.283(4), P1-N3 1.636(8), P1-N2 1.768 (7), P1-N1 1.792 (7), P2-N4 1.640 (7), P2-N2 1.791(6), P2-N1 1.793 (7), P3-N7 1.651 (7), P3-N5 1.795(7), P3-N6 1.799(6), P4-N8 1.630 (7), P4-N5 1.795 (7), P4-N6 1.801 (7), P5-N12 1.648(6), P5-N10 1.784(6), P5-N9 1.795 (7), P6-N11 1.645 (7), P6-N10 1.790(6), P6-N9 1.799(6), P7-N16 1.626 (7), P7-N13 1.788 (7), P7-N14 1.801 (7), P8-N15 1.645 (7), P8-N14 1.788 (7), P8-N13 1.794 (7), N1-C1 1....…”

Phosphines and related C–P bonded compounds

“…340 The formation of diphosphacyclobutenes in stereospecific [2 þ 2]-cycloaddition reactions of diphosphorus (P 2 ) with alkenes has been the subject of a theoretical study. 341 Studies of the reactivity of diphosphenes have included chalcogenation reactions of kinetically-stable diphosphenes with elemental sulfur, selenium and tellurium, leading to thia-, selena-and tellura-diphosphiranes, 342 the formation of a ferrocenyldiphosphine-platinum(0) complex, 343 the formation of a C 10 P 2 cationic cage system on protonation of the diphosphene C 5 Me 5 PQPC 5 Me 5 , 344 and the formation of a kineticallystabilised diphosphene anion-radical by the one-electron reduction of the diphosphene TbtPQPTbt (Tbt ¼ 2,4,6-tris[bis(trimethylsilyl)methyl] phenyl). 345 A successful protocol has been developed for the introduction of stable phosphaalkene units into oligoalkynes, leading to compounds of types (162) and (163), a new class of p-conjugated molecules.…”

Organophosphorus–Tellurium Chemistry: From Fundamentals to Applications

“…14 The dramatic increase in the P-Te-P bond angle with ring size for the heterocycles containing one tellurium atom, although expected, is particularly noteworthy: 54.1° (Mes*OP) 2 Te (21a) « 80.4° (AdP) 3 Te (22) Hz, indicative of a significant influence of the phosphorus substituent on this parameter, but the crystal structure was not reported. 35 More recently, however, the same group prepared orange crystals of the symmetrical derivative (Fc*P) 2 Te (21b, Fc* = 2,5-bis(3,5-di-tbutylphenyl)ferocenyl) by very slow oxidation of Fc*P=PFc* with elemental tellurium in benzene at 70 °C and determined the X-ray structure. 70 The acute P-Te-P bond angle of 52.21(3)° is similar to the value of 54.1° found for 21a; |d(P-Te)|= 2.506(1) Å for 21b, cf.…”