Reported are complexes of the formula Fe(dithiolate)-(CO) 2 (diphos) and their use to prepare hom... more Reported are complexes of the formula Fe(dithiolate)-(CO) 2 (diphos) and their use to prepare homo-and heterobimetallic dithiolato derivatives. The starting iron dithiolates were prepared by a one-pot reaction of FeCl 2 and CO with chelating diphosphines and dithiolates, where dithiolate = S 2 (CH 2 ) 2 2− (edt 2− ), S 2 (CH 2 ) 3 2− (pdt 2− ), S 2 (CH 2 ) 2 (C(CH 3 ) 2 ) 2− (Me 2 pdt 2− ) and diphos = cis-C 2 H 2 (PPh 2 ) 2 (dppv), C 2 H 4 (PPh 2 ) 2 (dppe), C 6 H 4 (PPh 2 ) 2 (dppbz), C 2 H 4 [P(C 6 H 11 ) 2 ] 2 (dcpe). The incorporation of 57 Fe into such building block complexes commenced with the conversion of 57 Fe into 57 Fe 2 I 4 ( i PrOH) 4 , which then was treated with K 2 pdt, CO, and dppe to give 57 Fe(pdt)(CO) 2 (dppe). NMR and IR analyses show that these complexes exist as mixtures of all-cis and trans-CO isomers, edt 2− favoring the former and pdt 2− the latter. Treatment of Fe(dithiolate)-(CO) 2 (diphos) with the Fe(0) reagent (benzylideneacetone)Fe(CO) 3 gave Fe 2 (dithiolate)(CO) 4 (diphos), thereby defining a route from simple ferrous salts to models for hydrogenase active sites. Extending the building block route to heterobimetallic complexes, treatment of Fe(pdt)(CO)
Reported are complexes of the formula Fe(dithiolate)-(CO) 2 (diphos) and their use to prepare hom... more Reported are complexes of the formula Fe(dithiolate)-(CO) 2 (diphos) and their use to prepare homo-and heterobimetallic dithiolato derivatives. The starting iron dithiolates were prepared by a one-pot reaction of FeCl 2 and CO with chelating diphosphines and dithiolates, where dithiolate = S 2 (CH 2 ) 2 2− (edt 2− ), S 2 (CH 2 ) 3 2− (pdt 2− ), S 2 (CH 2 ) 2 (C(CH 3 ) 2 ) 2− (Me 2 pdt 2− ) and diphos = cis-C 2 H 2 (PPh 2 ) 2 (dppv), C 2 H 4 (PPh 2 ) 2 (dppe), C 6 H 4 (PPh 2 ) 2 (dppbz), C 2 H 4 [P(C 6 H 11 ) 2 ] 2 (dcpe). The incorporation of 57 Fe into such building block complexes commenced with the conversion of 57 Fe into 57 Fe 2 I 4 ( i PrOH) 4 , which then was treated with K 2 pdt, CO, and dppe to give 57 Fe(pdt)(CO) 2 (dppe). NMR and IR analyses show that these complexes exist as mixtures of all-cis and trans-CO isomers, edt 2− favoring the former and pdt 2− the latter. Treatment of Fe(dithiolate)-(CO) 2 (diphos) with the Fe(0) reagent (benzylideneacetone)Fe(CO) 3 gave Fe 2 (dithiolate)(CO) 4 (diphos), thereby defining a route from simple ferrous salts to models for hydrogenase active sites. Extending the building block route to heterobimetallic complexes, treatment of Fe(pdt)(CO)
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