Bimetallic Clusters of Iron with Palladium and Platinum. Synthesis and Structures of Fe2(CO)9[M(PBut3)]2(M = Pd or Pt) and Fe2(CO)8[Pt(PBut3)]2(μ-H)2

Adams, Richard D.; Captain, Burjor; Pearl, William C.

doi:10.1021/ic061087d

Cited by 9 publications

(3 citation statements)

References 25 publications

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“…Complexes 4-M can be considered as metal-only Lewis pairs (MOLPs), in which the electron-rich zerovalent group 10 metal acts as the electron donor to the electron-accepting iron(0) center. Similar CO-bridged Ni/Pd/Pt(0)→Fe(CO) n MOLPs have been reported for [LNi 2 -(μ-CO) 2 -Fe(CO) 2 ] (L = neutral chelating ligand), , [LNi-(μ-CO) 2 -Fe(CO) 3 ], , [( t Bu 3 P) 2 M 2 -(μ-CO) 4 -Fe 2 (CO) 5 ] (M = Pd, Pd), and [(Ph 3 P)Pt-(μ-CO)-(μ-dppm)-Fe(CO) 3 ] (dppm = CH 2 (PPh 2 ) 2 ) …”

Section: Results and Discussionsupporting

confidence: 76%

Synthesis and Reactivity of Highly Electron-Rich Zerovalent Group 10 Diborabenzene Pogo-Stick Complexes

Dietz,

Arrowsmith,

Endres

et al. 2023

J. Am. Chem. Soc.

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A cyclic alkyl(amino)carbene (CAAC)-stabilized 1,4-diborabenzene (DBB, 1) reacts with the group 10 precursor [Ni(CO) 4 ] to yield the DBB pogo-stick complex [(η 6 -DBB)Ni-(CO)] (2) as a dark-green crystalline solid. The IR-spectroscopic and X-ray crystallographic data of 2 highlight the strong π-donor properties of the DBB ligand. The reaction of 1 with [M(nbe) 2 ] (M = Pd, Pt; nbe = norbornene) yields the unique zerovalent heavier group 10 arene pogo-stick complexes [(η 6 -DBB)M(nbe)] (3-M), isolated as dark-purple and black crystalline solids, respectively. 3-Pd and 3-Pt show strong near-IR (NIR) absorptions at 835 and 904 nm, respectively. Time-dependent density functional theory (TD-DFT) calculations show that these result from the S 0 →S 1 excitation, which corresponds to a transfer of electron density from a metal d orbital aligned with the z direction (d xz or d yz ) to a d orbital located in the xy plane (d xy or d x 2 −y 2 ), with the redshift for 3-Pt resulting from the higher spin-orbit coupling (SOC). In complex 2, electron donation from the nickel center into the carbonyl 2π* orbital destabilizes the DBB•••Ni interaction, resulting in an absorption at a higher energy. Complexes 2 and 3-M react with [Fe(CO) 5 ] to yield the doubly CO-bridged M(0)→ Fe(0) (M = Ni, Pd, Pt) metal-only Lewis pairs (MOLPs) 4-M as black (M = Ni, Pt) and dark-turquoise (M = Pd) crystalline solids. Furthermore, 3-Pt undergoes oxidative Sn−H addition with Ph 3 SnH to yield the corresponding Pt(II) stannyl hydride, [(η 6 -DBB)PtH(SnPh 3 )] (5).

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Section: Results and Discussionsupporting

confidence: 76%

Synthesis and Reactivity of Highly Electron-Rich Zerovalent Group 10 Diborabenzene Pogo-Stick Complexes

Dietz,

Arrowsmith,

Endres

et al. 2023

J. Am. Chem. Soc.

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“…Recent studies have shown that the magnetic moments of some 3d-TM (Fe, Co, and Ni) clusters are significantly larger than the corresponding bulk magnetizations [27][28][29][30][31][32][33]. Also some experimental [34] and theoretical [35,36] studies have focused on the Pd, Zr clusters and bimetallic compounds [37,38] of these two elements. The Pd compounds can be used as catalysts as it is the subject of many articles [39].…”

Section: Introductionmentioning

confidence: 99%

Structural, electronic and magnetic properties of small bimetallic zirconium–palladium clusters: Ab initio study

Javan

2015

Journal of Alloys and Compounds

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“…It is noteworthy that bimetallic catalysts have been applied to various organic reactions in the recent past and often such catalysts offered superior results in terms of efficiency and selectivity relative to the individual ones . Although, there exist some well‐characterized bimetallic Fe–Pd complexes in the literature, such complexes have not been investigated so far as catalysts for the Suzuki–Miyaura reactions. Thus, in order to enlarge this series and to widen the scope of metal‐containing phosphines as ligands, herein we have also explored the catalytic efficiency of the complex 1 /PdCl 2 system for the Suzuki–Miyaura cross‐coupling reactions of aryl halides with arylboronic acids.…”

Section: Introductionmentioning

confidence: 99%

Iron carbonyl complex containing bis[2‐(diphenylphosphino)phenyl]ether enhancing efficiency in the palladium‐catalyzed Suzuki–Miyaura reaction

Borah

Bhattacharyya

Das

2012

Applied Organom Chemis

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The reaction of [Fe3(CO)12] with bis[2‐(diphenylphosphino)phenyl]ether (DPEphos) in refluxing THF afforded a mononuclear complex, [Fe(CO)4(η1‐P‐DPEphos)] (1), as major product and a binuclear complex, [Fe2(CO)6(μ‐CO)(μ‐P,P‐DPEphos)] (2), as minor product respectively. The DPEphos ligand acts as a terminal P‐donor in complex 1 and a bridging P,P‐donor in complex 2. Complexes 1 and 2 were characterized by elemental analysis, fast atom bombardment mass spectrometry, FT‐IR, 1H and 31P{1H} NMR spectroscopy. The structure of complex 1 has been tentatively assigned by density functional theory calculations and its analogy with reported complexes. Combination of complex 1 and PdCl2 furnished an active catalyst for the Suzuki–Miyaura cross‐coupling reactions of various aryl halides with arylboronic acids. Interestingly, under the same experimental condition, complex 1/PdCl2 as catalyst showed superior activity over the DPEphos/PdCl2 system. Copyright © 2012 John Wiley & Sons, Ltd.

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Bimetallic Clusters of Iron with Palladium and Platinum. Synthesis and Structures of Fe₂(CO)₉[M(PBu^t₃)]₂(M = Pd or Pt) and Fe₂(CO)₈[Pt(PBu^t₃)]₂(μ-H)₂

Cited by 9 publications

References 25 publications

Synthesis and Reactivity of Highly Electron-Rich Zerovalent Group 10 Diborabenzene Pogo-Stick Complexes

Synthesis and Reactivity of Highly Electron-Rich Zerovalent Group 10 Diborabenzene Pogo-Stick Complexes

Structural, electronic and magnetic properties of small bimetallic zirconium–palladium clusters: Ab initio study

Iron carbonyl complex containing bis[2‐(diphenylphosphino)phenyl]ether enhancing efficiency in the palladium‐catalyzed Suzuki–Miyaura reaction

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