Stannylene or Metallastanna(IV)ocane: A Matter of Formalism

Brendler, Erica; Wächtler, Eberhard; Heine, Thomas; Zhechkov, Lyuben; Langer, Thor﻿s﻿ten; Pöttgen, Rainer; Hill, Anthony F.; Wagler, Jörg

doi:10.1002/anie.201007967

Cited by 48 publications

(36 citation statements)

References 57 publications

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“…Our search yielded four distinct families of complexes shown in Figure 1. 72,73,74,75 Because of the wide variety of elemental and ligand substitutions that it afforded, as well as because of its general ease of synthesis, we decided to focus our efforts on bis(pyridine-2-thiolate)-based family of heterobimetallic complexes shown in Figure 1a. In this family of complexes, a group 10 transition metal (Ni, Pd, Pt) and a group 14 (tetrel = Ge, Sn) are held together by two-bridging pyridine-2-thiolate ligands.…”

Section: Resultsmentioning

confidence: 99%

Intermetallic Nanocatalysts from Heterobimetallic Group 10–14 Pyridine-2-thiolate Precursors

et al. 2020

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Intermetallic compounds are atomically ordered inorganic materials containing two or more transition metals and main-group elements in unique crystal structures. Intermetallics based on group 10 and group 14 metals have shown enhanced activity, selectivity, and durability in comparison to simple metals and alloys in many catalytic reactions. While high-temperature solid-state methods to prepare intermetallic compounds exist, softer synthetic methods can provide key advantages, such as enabling the preparation of metastable phases or of smaller particles with increased surface areas for catalysis. Here, we study a generalized family of heterobimetallic precursors to binary intermetallics, each containing a group 10 metal and a group 14 tetrel bonded together and supported by pincer-like pyridine-2-thiolate ligands. Upon thermal decomposition, these heterobimetallic complexes form 10-14 binary intermetallic nanocrystals. Experiments and density functional theory (DFT) computations help in better understanding the reactivity of these precursors toward the synthesis of specific intermetallic binary phases. Using Pd2Sn as an example, we demonstrate that nanoparticles made in this way can act as uniquely selective catalysts for the reduction of nitroarenes to azoxyarenes, which highlights the utility of the intermetallics made by our method. Employing heterobimetallic pincer complexes as precursors toward binary nanocrystals and other metal-rich intermetallics provides opportunities to explore the fundamental chemistry and applications of these materials.

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Section: Resultsmentioning

confidence: 99%

Intermetallic Nanocatalysts from Heterobimetallic Group 10–14 Pyridine-2-thiolate Precursors

et al. 2020

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“…the E-TM bond can be described both as of Sn(IV)←Pd(0) (IV Z ) and Sn(II)→Pd(II) (IV L ) donor-acceptor nature (in addition to the intermediate Sn(III)-Pd(I) case (IV X ) with a perfect covalent bond and various other canonical forms which would require the setting of formal charges). 7 Gabbaï observed a similar dichotomy between two borderline cases in a set of 2-phosphinoaryl bridged Sb-Au complexes (V), and referred to this as σ-donor/acceptor confused behaviour of the ligand (ligands of L/Z-type, according to Green). 8 In IV, this donor/acceptor confusion is supported by the charge delocalisation within the N,S-bridging ligand (which thus gives rise to various resonance structures without formal charge), whereas in V the combination of the presence of a lone pair at Sb and the well known Lewis acidic properties of Sb(III) compounds 9 is responsible for this L/Z-type behaviour.…”

Section: Introductionmentioning

confidence: 87%

Group 10–group 14 metal complexes [E–TM]^IV: the role of the group 14 site as an L, X and Z-type ligand

et al. 2016

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A series of new complexes of a general motif [R2E(μ-N,S)2TM-L] (E: metalloid group 14 element; TM: group 10 metal; R: Cl, Ph, pyS, OH, (N,N,O)-chelating ligands; N,S: 1-methylimidazole-2-thiolate (methimazolyl, mt(-)), pyridine-2-thiolate (pyS(-)); L: PPh3, PCy3, pyS) was synthesised and characterised by single-crystal X-ray diffraction, multi-nuclear NMR spectroscopy ((1)H, (13)C, (31)P, (119)Sn), (119)Sn Mössbauer spectroscopy and quantum chemical calculations. The E-TM bonding situation in these compounds can be described with various resonance structures which comprise E(ii)→TM(ii), E(iii)-TM(i) and E(iv)←TM(0) features. Thus, in these complexes the atoms of the group 14 based ligand sites reveal L-, X- and Z-type ligand characteristics. A systematic comparison between structural and spectroscopic parameters as well as the results from NLMO analyses of structurally related compounds provided information about the differences in the E-TM bonding situation upon alteration of the metal atoms or ligand patterns. Under investigation are the structurally related compounds [Cl2Sn(μ-pyS)2TM-PPh3] (1: TM = Pd; 2: TM = Ni; 3: TM = Pt), [Cl2Ge(μ-pyS)2Pd-PPh3] (4) and, for in silico analysis, [Cl2Si(μ-pyS)2Pd-PPh3] (5), which indicate a pronounced shift of the E-TM bond electron pair towards TM for TM = Pt. Further complexes serve as representatives of these compounds with different bridging ligands {[Cl2Sn(μ-mt)2Pd-PPh3] (8)}, different trans-E-TM-bound ligands {[Cl2Sn(μ-pyS)2Pd-PCy3] (9), [Cl2Sn(μ-pyS)2Pd]4 (10)} and with different substituents at Sn (including penta- and hexacoordinated tin compounds), i.e., [R2Sn(μ-pyS)2Pd-PPh3] with R = Ph (6) and pyS (7), [(O,N,N)Sn(μ-pyS)2Pd-PPh3] (11) and (12) having two different (O,N,N) tridentate ligands, and [(μ-OH)ClSn(μ-pyS)2Pd-PPh3]2 (13). The latter series indicates a shift of the E-TM (= Sn-Pd) bond electron pair towards Pd upon transition from penta- to hexacoordinated tin compounds.

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“…In contrast, structurally characterized examples of mononuclear complexes of metal fragments with dihalotetrels are limited to dihalocarbenes3 and one “PtPbCl 2 ” complex from our laboratories 4. Recent work by the groups of Deelman5 and Wagler6 led to the synthesis of a number of palladium/platinum complexes containing SnCl 2 ligands, however, in all cases these MSn bonds were bridged by ditopic ligands, creating considerable ambiguity in terms of the bonding situation (M→Sn/M←Sn/MSn) and the oxidation states of the M and Sn centers. Consequently, we sought to prepare such complexes containing SnCl 2 (and GeCl 2 ) without bridging elements, in order to eliminate the ambiguity.…”

Section: Introductionmentioning

confidence: 99%

Platinum Complexes Containing Pyramidalized Germanium and Tin Dihalide Ligands Bound through σ,σ ME Multiple Bonds

Hupp

Kroll

et al. 2014

Chemistry A European J

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Stannylene or Metallastanna(IV)ocane: A Matter of Formalism

Cited by 48 publications

References 57 publications

Intermetallic Nanocatalysts from Heterobimetallic Group 10–14 Pyridine-2-thiolate Precursors

Intermetallic Nanocatalysts from Heterobimetallic Group 10–14 Pyridine-2-thiolate Precursors

Group 10–group 14 metal complexes [E–TM]^IV: the role of the group 14 site as an L, X and Z-type ligand

Platinum Complexes Containing Pyramidalized Germanium and Tin Dihalide Ligands Bound through σ,σ ME Multiple Bonds

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Stannylene or Metallastanna(IV)ocane: A Matter of Formalism

Cited by 48 publications

References 57 publications

Intermetallic Nanocatalysts from Heterobimetallic Group 10–14 Pyridine-2-thiolate Precursors

Intermetallic Nanocatalysts from Heterobimetallic Group 10–14 Pyridine-2-thiolate Precursors

Group 10–group 14 metal complexes [E–TM]IV: the role of the group 14 site as an L, X and Z-type ligand

Platinum Complexes Containing Pyramidalized Germanium and Tin Dihalide Ligands Bound through σ,σ ME Multiple Bonds

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Group 10–group 14 metal complexes [E–TM]^IV: the role of the group 14 site as an L, X and Z-type ligand