Ternary Rare‐Earth Transition‐Metal Polyhydride Cluster Compounds

Bauer, Tobias; Wagner, Frank R.; Kempe, Rhett

doi:10.1002/chem.201301290

Cited by 14 publications

(14 citation statements)

References 48 publications

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“…[30] Both metallocene dihydrides are known to form heterometallic compounds with bridging hydride interactions: Cp2ZrH2 gives stable adducts with Mg, Zn and Al hydrides, [31] while Cp2WH2 has been extensively explored in combination with many cationic late metal centers, including Al, [32] Rh, [33] Pt [34] and rare earth metals. [35] Cp2WH2 is also a good ligand for isolated Cu and Ag centers, [36] while to our knowledge there is no precedent for W-Au dihydrides.…”

Section: Introductionmentioning

confidence: 99%

Hydride Transfer to Gold: Yes or No? Exploring the Unexpected Versatility of Au⋅⋅⋅H−M Bonding in Heterobimetallic Dihydrides

Rocchigiani

Klooster

Coles

et al. 2020

Chemistry A European J

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The potential for coordination and H-transfer from Cp2MH2 (M = Zr, W) to gold(I) and gold(III) complexes was explored in a combined experimental and computational study. [(L)Au] + cations react with Cp2WH2 giving [(L)Au(κ 2 -H2WCp2)] + (L = IPr (1), cyclic (alkyl)(amino)carbene (2), or phosphines PPh3 (3) and Dalphos-Me (4) [IPr = 1,3-bis(diisopropylphenyl)imidazolylidene; Dalphos-Me = di(1-adamantyl)-2-(dimethylamino)phenyl-phosphine], while [Au(DMAP)2] + (DMAP = p-dimethylaminopyridine) affords the C2-symmetric [Au(κ-H2WCp2)2] + (5). The Dalphos complex 4 can be protonated to give the bicationic adduct 4H, showing Au(I) … H + -N hydrogen bonding. The gold(III) Lewis acid [(C^N-CH)Au(C6F5)(OEt2)] + binds Cp2WH2 to give an Au-H-W σ-complex. By contrast, the pincer species [(C^N^C)Au] + adds Cp2WH2 by a purely dative W→Au bond, without Au···H interaction. The biphenyl-based chelate [(C^C)Au] + forms [(C^C)Au(μ-H)2WCp2] + , with two 2-electron-3-centre W-H … Au interactions and practically no Au-W donor acceptor contribution. In all these complexes strong but polarised W-H bonds are maintained, without H-transfer to gold. On the other hand, the reactions of Cp2ZrH2 with gold complexes led in all cases to rapid H-transfer and formation of gold hydrides. Relativistic DFT calculations were used to rationalize the striking reactivity and bonding differences in these heterobimetallic hydride complexes along with an analysis of their characteristic NMR parameters and UV-Vis absorption properties.

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Section: Introductionmentioning

confidence: 99%

Hydride Transfer to Gold: Yes or No? Exploring the Unexpected Versatility of Au⋅⋅⋅H−M Bonding in Heterobimetallic Dihydrides

Rocchigiani

Klooster

Coles

et al. 2020

Chemistry A European J

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“…Additionally, a covalent direct W Lu interaction was indicated by ELI-D (electron localizability indicator) analysis. It was pointed out that concerning the broader strategy of building higher aggregated ternary lanthanide-transition metal polyhydride clusters, the hydride precursors Cp 2 MH 2 represent promising transition-metal building blocks [115]. hexanuclear PMe 3 -free Y 4 /M 2 complexes as illustrated in Scheme 138 [116].…”

Section: Heterobimetallic Organolanthanide Complexesmentioning

confidence: 99%

“…Thus, the reaction of 1.5 equiv. of Cp 2 WH 2 with Lu(OAr)R 2 (THF) 2 (ArO = 2,6-di-tertbutyl-phenolate, R = CH 2 SiMe 3 ) in benzene at room temperature gave the heteromultimetallic polyhydride cluster compound shown in Scheme 135 in 75% yield [115].…”

Section: Heterobimetallic Organolanthanide Complexesmentioning

confidence: 99%

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Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2013

Edelmann

2015

Coordination Chemistry Reviews

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“…At the present time source function (SF), [12, 13, 14 and ref. therein] delocalization index (DI) and electron localizability indicator (ELI‐D) are the most often applied in the capacity of continuous bonding indicators. In turn, it was recently proposed to use a noncovalent interaction (NCI) index, based on the reduced electron density gradient (RDG), to characterize and visualize different types of weak interactions .…”

Section: Introductionmentioning

confidence: 99%

Experimental and Theoretical AIM and NCI Index Study of Substituted Arene Tricarbonyl Complexes of Chromium(0)

et al. 2016

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The molecular structure and charge density distribution in the crystals of (η6‐2,3‐phenyl‐1,2‐oxazolidine‐5‐carbonitrile)‐ tricarbonyl‐chromium (1) and (η6‐2‐t‐Butyl‐3‐phenyl‐1,2‐ oxazolidine‐5‐carbonitrile)‐tricarbonyl‐chromium (2) derived from the high‐resolution single crystal X‐ray diffraction data at 100 K is reported together with DFT calculations of these molecules. The noncovalent interaction (NCI) index was tested for evaluation of the hapticity of arene ligands in 1 and 2. In contrast to AIM (the quantum theory of atoms in molecules) bond‐path analysis the NCI index adequately describes electronic aspects of the Cr‐arene interactions. These results are in agreement with analysis data of source function (SF) and delocalization index (DI). Thus the NCI index along with the SF and DI can be applied for investigation of metal‐ligand interactions which are characterized by very flat change of electron density.

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Ternary Rare‐Earth Transition‐Metal Polyhydride Cluster Compounds

Cited by 14 publications

References 48 publications

Hydride Transfer to Gold: Yes or No? Exploring the Unexpected Versatility of Au⋅⋅⋅H−M Bonding in Heterobimetallic Dihydrides

Hydride Transfer to Gold: Yes or No? Exploring the Unexpected Versatility of Au⋅⋅⋅H−M Bonding in Heterobimetallic Dihydrides

Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2013

Experimental and Theoretical AIM and NCI Index Study of Substituted Arene Tricarbonyl Complexes of Chromium(0)

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