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Tungsten Carbonyl Complexes of 1 H ‐Diphosphirenes and Diphosphirenylium Salts
Author(s) -
Bourissou Didier,
Canac Yves,
Gornitzka Heinz,
Marsden Colin J.,
Baceiredo Antoine,
Bertrand Guy
Publication year - 1999
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199909)1999:9<1479::aid-ejic1479>3.0.co;2-z
Subject(s) - chemistry , medicinal chemistry , sodium tetraphenylborate , trifluoromethanesulfonate , lithium (medication) , salt (chemistry) , inorganic chemistry , lithium aluminium hydride , nucleophile , chloride , hydride , tetraphenylborate , catalysis , organic chemistry , hydrogen , ion , medicine , endocrinology
The 1,1,3‐tris(diisopropylamino)diphosphirenium salt 1 reacts with lithium aluminium hydride leading to the P ‐hydrogeno‐ C ‐phosphinophosphaalkenes 2 , which on treatment with a catalytic amount of BF 3 ·OEt 2 afford the 1,3‐bis(diisopropylamino)‐1 H ‐diphosphirene 3 . The corresponding η 1 ‐coordinated 1 H ‐diphosphirene 6 can be prepared by treatment of 2 or 3 with one equivalent of [W(CO) 5 (thf)]. Alternatively, the diphosphirenium salt 1 reacts with an excess of [W(CO) 5 (thf)], affording the corresponding η 1 ‐coordinated diphosphirenium salt complex 4 , which is converted into the P ‐hydrogenophosphaalkene complex 5 with lithium aluminium hydride. The dinuclear tungsten complexes 7 and 8 are obtained by treatment of the free 1 H ‐diphosphirene 3 with two equivalents of [W(CO) 5 (thf)] or one equivalent of [W(CO) 4 (thf) 2 ], respectively. Compound 6 reacts with two equivalents of hydrogen chloride, giving the 1‐chloro‐3‐diisopropylamino‐1 H ‐diphosphirene 9 , which can be subsequently converted into the 1‐diisopropylamino‐, 1‐azido, or 1‐phenyl‐3‐diisopropylamino‐1 H ‐diphosphirenes 6 , 10 and 11 by nucleophilic substitution with diisopropylamine, azidotrimethylsilane or sodium tetraphenylborate, respectively. The [η 2 ‐(3‐diisopropylaminodiphosphirenylium salt)·W(CO) 5 ] complexes 12a‐c can be prepared by reaction of 9 with silver trifluoromethanesulfonate, aluminium or gallium trichloride or, alternatively, by treatment of 6 with two equivalents of trifluoromethanesulfonic acid. Reaction of 12a with diisopropylamine, water, bis(triphenylphosphoranylidene)ammonium chloride or tetrabutylammonium fluoride gives the corresponding 1 H ‐diphosphirene complexes 6 , 13 , 9 , or 14 , respectively. Compound 12a also reacts with one or two equivalents of [W(CO) 5 (thf)], leading to the di‐ and tri‐nuclear complexes 15 and 16 , respectively.