title: Ferrous Carbonyl Dithiolates as Precursors to FeFe, FeCo, and FeMn Carbonyl Dithiolates.
abstract: 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 FeCl2and CO with chelating diphosphines and dithiolates, where dithiolate = S2(CH2)22-(edt2-), S2(CH2)32-(pdt2-), S2(CH2)2(C(CH3)2)2-(Me2pdt2-) and diphos =cis-C2H2(PPh2)2(dppv), C2H4(PPh2)2(dppe), C6H4(PPh2)2(dppbz), C2H4[P(C6H11)2]2(dcpe). The incorporation of57Fe into such building block complexes commenced with the conversion of57Fe into57Fe2I4(iPrOH)4, which then was treated with K2pdt, CO, and dppe to give57Fe(pdt)(CO)2(dppe). NMR and IR analyses show that these complexes exist as mixtures of all-cis and trans-CO isomers, edt2-favoring the former and pdt2-the latter. Treatment of Fe(dithiolate)(CO)2(diphos) with the Fe(0) reagent (benzylideneacetone)Fe(CO)3gave Fe2(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)2(dppe) with [(acenaphthene)Mn(CO)3]+gave [(CO)3Mn(pdt)Fe(CO)2(dppe)]+([3d(CO)]+). Reduction of [3d(CO)]+with BH4-gave theCs-symmetric μ-hydride (CO)3Mn(pdt)(H)Fe(CO)(dppe) (H3d). Complex H3dis reversibly protonated by strong acids, the proposed site of protonation being sulfur. Treatment of Fe(dithiolate)(CO)2(diphos) with CpCoI2(CO) followed by reduction by Cp2Co affords CpCo(dithiolate)Fe(CO)(diphos) (4), which can also be prepared from Fe(dithiolate)(CO)2(diphos) and CpCo(CO)2. Like the electronically related (CO)3Fe(pdt)Fe(CO)(diphos), these complexes undergo protonation to afford the μ-hydrido complexes [CpCo(dithiolate)HFe(CO)(diphos)]+. Low-temperature NMR studies indicate that Co is the kinetic site of protonation.
authors.affiliation: Department of Chemistry, University of Illinois , Urbana, Illinois 61801, United States.
authors.forename: Maria E
authors.initials: ME
authors.lastname: Carroll
authors.affiliation: Department of Chemistry, University of Illinois , Urbana, Illinois 61801, United States.
authors.forename: Jinzhu
authors.initials: J
authors.lastname: Chen
authors.affiliation: Department of Chemistry, University of Illinois , Urbana, Illinois 61801, United States.
authors.forename: Danielle E
authors.initials: DE
authors.lastname: Gray
authors.affiliation: Department of Chemistry, University of Illinois , Urbana, Illinois 61801, United States.
authors.forename: James C
authors.initials: JC
authors.lastname: Lansing
authors.affiliation: Department of Chemistry, University of Illinois , Urbana, Illinois 61801, United States.
authors.forename: Thomas B
authors.initials: TB
authors.lastname: Rauchfuss
authors.affiliation: Department of Chemistry, University of Illinois , Urbana, Illinois 61801, United States.
authors.forename: David
authors.initials: D
authors.lastname: Schilter
authors.affiliation: Department of Chemistry, University of Illinois , Urbana, Illinois 61801, United States.
authors.forename: Phillip I
authors.initials: PI
authors.lastname: Volkers
authors.affiliation: Department of Chemistry, University of Illinois , Urbana, Illinois 61801, United States.
authors.forename: Scott R
authors.initials: SR
authors.lastname: Wilson