1350883-58-7

Upstream product

• 2049-55-0 triphenylphosphine borane 
• 82265-64-3 syn-[5,6-dimethyl-2,3-bis(methoxycarbonyl)-7-phenyl-7-phosphanorbornadiene]pentacarbonyltungsten 
• 61300-75-2 phenylphosphine pentacarbonyltungsten⁽⁰⁾ 
• 1333-74-0 hydrogen 

Downstream Products

• 61300-75-2 phenylphosphine pentacarbonyltungsten⁽⁰⁾ 

Relevant academic research and scientific papers

Simple access to tungsten-stabilized disecondary diphosphines

Transient terminal phosphinidene complexes [RP-W(CO)5] dimerize in the presence of copper chloride, and the dimers react in situ with triphenylphosphine-borane to give the disecondary diphosphine complexes [RPH-PHR][W(CO)5]2. When R = CH2CH 2Cl, a cyclization takes place to give the diphosphirane complex. A 1,2-diphospholane is obtained for R = Ph by further reaction with 1,3-dibromopropane in the presence of aqueous K2CO3.

Insertion of phosphinidene complexes into the P-H bond of secondary phosphine oxides: A new version of the phospha-Wittig synthesis of P=C double bonds

Terminal phosphinidene complexes [RP-W(CO)5], as generated at 60 °C in the presence of copper chloride from the appropriate 7-phosphanorbornadiene complexes, react with secondary phosphine oxides Ar2P(O)H to give the insertion products into the P-H bonds. After metalation with NaH, these products react with aldehydes to give the corresponding phosphaalkenes which are trapped by dimethylbutadiene.

Reaction of terminal phosphinidene complexes with dihydrogen

The reaction of H2 with [RP-W(CO)5] (R = Ph, Me) above 120 °C leads, first, to the secondary diphosphine complex (RPH-PHR)(W(CO)5)2 and then to the primary phosphine complex (RPH2)(W(CO)5). On the basis of DFT calculations, the mechanism most likely involves the addition of H2 to the P-W bond, followed by the formation of the radical [RPH-W(CO)5] ? by homolysis of the W-H bond. In the case of [PhNHP-W(CO) 5], the hydrogenolysis takes place at the P-N bond and ultimately produces the secondary diaminophosphine complex ((PhNH)2PH)(W(CO) 5).