Trapping of Brønsted acids with a phosphorus-centered biradicaloid – synthesis of hydrogen pseudohalide addition products

Abstract

The trapping of classical hydrogen pseudohalides (HX, X = pseudohalogen = CN, N3, NCO, NCS, and PCO) utilizing a phosphorus-centered cyclic biradicaloid, [P(μ-NTer)]2, are reported. These formal Brønsted acids were...

A comparative study of biradicaloids as ligands in iron tetracarbonyl complexes

“…[P(µ-N-TerCl)]2 was synthesized according to a modified literature procedure. 17 Mg turnings can be activated by stirring under argon atmosphere for several days using a glass-covered magnetic-stirring bar. [P(µ-N-TerCl)]2 (6.43 g, 8.16 mmol) and Mg turnings (2.87 g, 118 mmol) were combined in a Schlenk flask.…”

The dialkylcarbonate route to ionic liquids: purer, safer, greener?

“…HCN, HN 3 , HNCO, HNCS, HPCO), Beer et al prepared with excellent yields [N 4441 ][NCS] and [N 4441 ][PCO], using commercial solution of [N 4441 ][MeOCO 2 ] and trimethylsilyl-thiocyanate TMS-SCN, and trimethylsilyl phosphine TMS 3 P (Table 5, entry 17). 115…”

“…These salts were then converted in hexasulfide, triselenide, and dodecatelluride salts (Table 5, entry 12). 35 ] where E = S or Se or Te Finger et al 35,110 In their study about generation of organic electron-donors from air-stable precursors, Tintori et 115 De Feo et al patented the use of [N 8881 ][RCO 2 ] ionic liquids (R is an alkyl chain (4 to 8 carbons)) made by anion exchange with commercial [N 8881 ][MeOCO 2 ], as the major compound of lubricants (Table 6, entry 18). 116…”

Concerted addition of aldehydes to the singlet biradical [P(μ-NTer)]2

“…31 These formal hetero-cyclobutanediyls are known to readily activate small molecules in formal 1,1-or 1,3-addition reactions. As singlet biradicals, they can undergo either stepwise radical reactions 29,32,33 or concerted ("closed-shell") reactions, 17,19,[34][35][36][37][38][39][40] depending on the strength of the antiferromagnetic coupling between the radical electrons and the reaction conditions. 8 It is worthy to note, though, that the classification as either radical or concerted reaction is frequently based on phenomenological observations alone, while the actual mechanisms of the addition reactions to hetero-cyclobutanediyls have often not been investigated in detail yet.…”