Reductive elimination of halogens assisted by phosphine ligands in Fe(CO)4X2 (X=I,Br) complexes

Bellachioma, Gianfranco; Cardaci, Giuseppe; Macchioni, Alceo; Venturi, Chiara; Zuccaccia, Cristiano

doi:10.1016/j.jorganchem.2006.05.041

Cited by 27 publications

(23 citation statements)

References 47 publications

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“… 15 Complexes of formula FeX 2 (CO) 2 (PR 3 ) 2 , in which all the ligands are monodentate, exist as both the cis,cis,trans and all-trans isomers, depending on the phosphine ligand. 21 …”

Section: Introductionmentioning

confidence: 99%

Ferrous Carbonyl Dithiolates as Precursors to FeFe, FeCo, and FeMn Carbonyl Dithiolates

et al. 2014

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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 FeCl2 and 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 of 57Fe into such building block complexes commenced with the conversion of 57Fe into 57Fe2I4(iPrOH)4, which then was treated with K2pdt, CO, and dppe to give 57Fe(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)3 gave 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 the Cs-symmetric μ-hydride (CO)3Mn(pdt)(H)Fe(CO)(dppe) (H3d). Complex H3d is 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.

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“… 15 Complexes of formula FeX 2 (CO) 2 (PR 3 ) 2 , in which all the ligands are monodentate, exist as both the cis,cis,trans and all-trans isomers, depending on the phosphine ligand. 21 …”

Section: Introductionmentioning

confidence: 99%

Ferrous Carbonyl Dithiolates as Precursors to FeFe, FeCo, and FeMn Carbonyl Dithiolates

et al. 2014

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“…Samples were mounted on a glass fibre using grease and were exposed, as the phi axis was spun (20 • s -1 ), for a period of 20 min. (1) formed and were collected by vacuum filtration. These crystals rapidly desolvated upon removal from the mother liquor (precluding elemental analysis).…”

Section: General Proceduresmentioning

confidence: 99%

“…2,7, 8 Recent results have described the reductive elimination of halogens from Au(III) centres via UV photolysis, using alkenes to trap the released halogens. 1,5,9 In this light, we recently reported the first coordination polymers with the Au(III)-containing building block [AuBr 2 (CN) 2 ] -, 10 with the intention of using the Br-Au-Br moiety as a structuredirecting unit via intermolecular Br ◊ ◊ ◊ Br interactions and influencing physical properties such as birefringence. 10 The related linear Au(I)-containing [Au(CN) 2 ] --based coordination polymers have been much more developed, 11 with such materials ex-hibiting interesting magnetic, 12,13 luminescent 14 or birefringent 15,16 properties.…”

Section: Introductionmentioning

confidence: 99%

Thermally triggered reductive elimination of bromine from Au(iii) as a path to Au(i)-based coordination polymers

Ovens

Leznoff

2011

Dalton Trans.

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Four new [AuBr(2)(CN)(2)](-)-based coordination polymers, Zn(pyz)(NCMe)(2)[AuBr(2)(CN)(2)](2) (1; pyz = pyrazine), Co(pyz)[AuBr(2)(CN)(2)](2)·H(2)O (2) and [M(bipy)(2)(AuBr(2)(CN)(2))][(n)Bu(4)N][AuBr(2)(CN)(2)](2) (bipy = 4,4'-bipyridine), where M = Co (5) and Zn (6), were synthesized and three of them structurally characterized. 1 forms 1-D chains connected by pyz ligands while isostructural 5 and 6 form 3-D frameworks via [AuBr(2)(CN)(2)](-) and bipy linkers. Aqueous suspensions of 2, 5 and 6 or their precursors in situ (preferred) were heated hydrothermally to 125 °C, triggering the reductive elimination of bromine from the Au(III) centres, which yielded the [Au(CN)(2)](-)-based coordination polymers M(pyz)[Au(CN)(2)](2), where M = Zn (3) or Co (4) and Zn(bipy)[Au(CN)(2)][Au{Br(0.68)(CN)(0.32)}CN] (7), or a mixture of cyanoaurate(I)-containing products in the case of 5 and 6. The structural characterization of 3 revealed a [Au(CN)(2)](-)/pyz-based framework similar to previously reported Cu(pyz)[Au(CN)(2)](2), whereas 7 formed an intricate network consisting of individual 2-D networks held together by AuAu interactions and featuring the rare [AuBrCN](-) unit. The kinetics of the thermally-induced reductive elimination of Br(2) from K[AuBr(2)(CN)(2)] in 1-BuOH yielded a t(½) of approx. 10 min to 4 h from 98 to 68 °C, and activation parameters of ΔH(‡) = 131(15) kJ mol(-1) and ΔS(‡) = 14.97(4) kJ K(-1)mol(-1), indicating that the elimination of the halogen provides the highest barrier to activation.

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“…Subsequent to this, Pań kowski and Bigorgne [7] examined the solution photochemical isomerization of Fe(CO) 2 X 2 (PMe 3 ) 2 , where X = Cl, Br and I, and established that the cis, cis, trans isomer transforms to the trans, trans, trans (alltrans) isomer upon exposure to sunlight, while the temperature dependent back reaction occurred in the dark. Bellachioma et al have used the photochemical transformation of cis, cis, trans Fe(CO) 2 I 2 (PMe 3 ) 2 for the synthesis of the all-trans isomer [8]. The analogous photochemical transformation of cis, cis, trans-Ru(CO) 2 -X 2 L 2 , where X = I, Br, or Cl and L = PR 3 or AsR 3 has been reported by Mawby and coworkers [9].…”

Section: Introductionmentioning

confidence: 96%

Frozen matrix photolysis of Group VIII M(CO)2Cl2L2 derivatives: Direct observation of CO-loss species and photochemical isomerization

Bitterwolf¹

2008

Journal of Organometallic Chemistry

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Reductive elimination of halogens assisted by phosphine ligands in Fe(CO)4X2 (X=I,Br) complexes

Cited by 27 publications

References 47 publications

Ferrous Carbonyl Dithiolates as Precursors to FeFe, FeCo, and FeMn Carbonyl Dithiolates

Ferrous Carbonyl Dithiolates as Precursors to FeFe, FeCo, and FeMn Carbonyl Dithiolates

Thermally triggered reductive elimination of bromine from Au(iii) as a path to Au(i)-based coordination polymers

Frozen matrix photolysis of Group VIII M(CO)2Cl2L2 derivatives: Direct observation of CO-loss species and photochemical isomerization

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