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Title: Metal-only Lewis pairs between group 10 metals and Tl(I) or Ag(I): insights into the electronic consequences of Z-type ligand binding

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/c5sc03104d· OSTI ID:1624926
 [1];  [1];  [2];  [3];  [1];  [4];  [1]
  1. Univ. of California, San Diego, La Jolla, CA (United States)
  2. Lamar Univ., Beaumont, TX (United States)
  3. Univ. of Glasgow, Scotland (United Kingdom)
  4. Max-Planck-Inst. for Chemical Energy Conversion (Germany); Cornell Univ., Ithaca, NY (United States)
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Complexes bearing electron rich transition metal centers, especially those displaying coordinative unsaturation, are well-suited to form reverse-dative σ-interactions with Lewis acids. Herein we demonstrate the generality of zerovalent, group 10 m-terphenyl isocyanide complexes to form reverse-dative σ-interactions to Tl(I) and Ag(I) centers. Structural and spectroscopic investigations of these metal-only Lewis pairs (MOLPs) has allowed insight into the electronic consequences of Lewis-acid ligation within the primary coordination sphere of a transition metal center. Treatment of the bis-isocyanide complex, Pt(CNArDipp2)2 (ArDipp2 = 2,6-(2,6-(i-Pr)2C6H3)2C6H3) with TlOTf (OTf = [O3SCF3]–) yields the Pt/Tl MOLP [TlPt(CNArDipp2)2]OTf (1). 1H NMR and IR spectroscopic studies on 1, and its Pd congener [TlPd(CNArDipp2)2]OTf (2), demonstrate that the M → Tl interaction is labile in solution. However, treatment of complexes 1 and 2 with Na[BArF4] (ArF = 3,5-(CF3)2C6H3) produces [TlPt(CNArDipp2)2]BArF4 (3) and [TlPd(CNArDipp2)2]BArF4 (4), in which Tl(I) binding is shown to be static by IR spectroscopy and, in the case of 3, 195Pt NMR spectroscopy as well. This result provides strong evidence that the M → Tl linkages can be attributed primarily to σ-donation from the group 10 metal to Tl, as loss of ionic stabilization of Tl by the triflate anion is compensated for by increasing the degree of M → Tl σ-donation. In addition, X-ray Absorption Near-Edge Spectroscopy (XANES) on the Pd/Tl and Ni/Tl MOLPs, [TlPd(CNArDipp2)2]OTf (2) and [TlNi(CNArMes2)3]OTf, respectively, is used to illustrate that the formation of a reverse-dative σ-interaction with Tl(I) does not alter the spectroscopic oxidation state of the group 10 metal. Also reported is the ability of M(CNArDipp2)2 (M = Pt, Pd) to form MOLPs with Ag(I), yielding the complexes [AgM(CNArDipp2)2]OTf (5, M = Pt; 6, M = Pd). As was determined for the Tl-containing MOLPs 1–4, it is shown that the spectroscopic oxidation states of the group 10 metal in 5 and 6 are essentially unchanged compared to the zerovalent precursors M(CNArDipp2)2. However, in the case of 5 and 6, the formation of a dative M → Ag σ-bonding interaction facilitates the binding of Lewis bases to the group 10 metal trans to Ag, illustrating the potential of acceptor fragments to open up new coordination sites on transition metal complexes without formal, two-electron oxidation.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Sponsoring Organization:
USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Max Planck Foundation; National Institutes of Health (NIH); National Institute of General Medical Sciences (NIGMS)
Grant/Contract Number:
AC02-76SF00515; P41GM103393
OSTI ID:
1624926
Journal Information:
Chemical Science, Vol. 6, Issue 12; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 31 works
Citation information provided by
Web of Science

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Cited By (12)

Stabilized Carbenium Ions as Latent, Z‐type Ligands journal October 2019
Cooperative activation of X–H (X = H, C, O, N) bonds by a Pt(0)/Ag( i ) metal-only Lewis pair journal January 2019
Monomeric Chini‐Type Triplatinum Clusters Featuring Dianionic and Radical‐Anionic π*‐Systems journal August 2016
Stabilized Carbenium Ions as Latent, Z‐type Ligands journal December 2019
A cooperative pathway for water activation using a bimetallic Pt 0 –Cu I system journal January 2016
Comparison of nucleophilic- and radical-based routes to the formation of manganese-main group element single bonds journal January 2017
Bimetallic nickel-lutetium complexes: tuning the properties and catalytic hydrogenation activity of the Ni site by varying the Lu coordination environment journal January 2019
A Scandium Metalloligand‐Based Heterobimetallic Pd−Sc Complex: Electronic Tuning Through a Very Short Pd→Sc Dative Bond journal June 2019
An Antimony(V) Dication as a Z‐Type Ligand: Turning on Styrene Activation at Gold journal June 2019
Dinitrogen binding, P 4 -activation and aza-Büchner ring expansions mediated by an isocyano analogue of the CpCo(CO) fragment journal January 2016
An Antimony(V) Dication as a Z‐Type Ligand: Turning on Styrene Activation at Gold journal July 2019
Heterobimetallic scandium–group 10 metal complexes with LM → Sc (LM = Ni, Pd, Pt) dative bonds journal January 2020

Linked Research (10)

Figures / Tables (16)

Scheme 1(p. 2)figure Scheme 1
Fig. 1(p. 3)figure Fig. 1
Fig. 2(p. 3)figure Fig. 2
Fig. 3(p. 3)figure Fig. 3
Fig. 4(p. 3)figure Fig. 4
Fig. 5(p. 4)figure Fig. 5
Table 1(p. 4)table Table 1
Fig. 6(p. 5)figure Fig. 6
Fig. 7(p. 5)figure Fig. 7
Fig. 10(p. 6)figure Fig. 10
Fig. 8(p. 6)figure Fig. 8
Fig. 9(p. 6)figure Fig. 9
Scheme 2(p. 6)figure Scheme 2
Table 2(p. 6)table Table 2
Fig. 11(p. 7)figure Fig. 11
Fig. 12(p. 8)figure Fig. 12

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