skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Reactivity of ruthenium complexes towards organogallium reagents: Gallium as a Z-type ligand or as a gallate counterion
The reaction of RuHCl(PPh3)3 with GaMe3 gives rise to the arene complex [(η6-C6H6)Ru(PPh3)(PPh2-o-C6H4-GaClMe], 1, with the Ga atom making part of an in situ generated ambiphilic phosphinogallyl ligand in a five-membered ruthenagallacycle ring with a tetracoordinate gallium. In the presence of excess GaMe3, 1 forms complex [(η6-C6H6)Ru(PPh3)(PPh2-o-C6H4-GaMe][GaMe3Cl], 2 also bearing a phosphinogallyl ligand. Crystals suitable for single-crystal X-ray diffraction were obtained of complex 2′, [(η6-C6H6)Ru(PPh3)(PPh2-o-C6H4-GaMe][GaMe2Cl2], showing an ion pair with two Ga atoms in different coordination environments: the first with a coordination number of three makes part of a five-membered ruthenagallacyle ring, while the second Ga atom is a gallate anion. In both complexes 1 and 2, the Ga atom binds to Ru as a σ-acceptor Z-type ligand. DFT calculations are in good agreement with the experimental single crystal X-ray diffraction data and provide Ru-Ga Wiberg bond indexes of 0.38 and 0.50, for 1 and 2 respectively. In contrast, treatment of RuHCl(PPh3)3 with GaMeCl2 and of RuCl2(PPh3)3 with GaMe3 gives rise to gallate species [(η6-C6H6)Ru(PPh3)2H][GaMeCl3], 3, and [(η6-C6H6)Ru(PPh3)2Me][GaMe2Cl2], 4, respectively.  more » « less
Award ID(s):
2145588
PAR ID:
10511509
Author(s) / Creator(s):
; ; ; ;
Publisher / Repository:
Elsevier
Date Published:
Journal Name:
Polyhedron
Volume:
247
Issue:
C
ISSN:
0277-5387
Page Range / eLocation ID:
116703
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; (, Organometallics)
    The coupling of carbon dioxide and ethylene to generate value added chemicals has been part of recent fundamental advances to improve sustainability in commercial chemical synthons. A formal zerovalent triphosphine ligated ruthenium complex, (tBuP(CH2CH2PEt2)2)Ru(κ-S-DMSO)(C2H4), was found to promote CO2 activation, affording products derived from both a 1:1 and 1:2 ethylene to CO2 coupling stoichiometry. The equimolecular coupling reaction selectively afforded a five-membered ruthenium lactone species, (tBuP(CH2CH2PEt2)2)Ru(κ-S-DMSO)(κ-C,κ-O-CH2CH2CO2), under low CO2 pressure. At higher CO2 pressure, the ruthenium lactone complex activated a second equivalent of CO2, yielding a dimeric methylmalonate ruthenium compound, [(tBuP(CH2CH2PEt2)2)Ru(μ2, κ1-O, κ2-O,O-O2CCHCH3CO2)]2. Both carbon dioxide activation products were characterized by X-ray diffraction. Preliminary mechanistic studies suggest that reversible β-H elimination is a key process in conversion between the two ruthenium carboxylate species. A rare formally zerovalent ruthenium coordination compound stabilized only by ethylene and DMSO ligands was also isolated and characterized. 
    more » « less
  2. ; ; ; ; ; ; (, Dalton Transactions)
    A series of Ni( ii ), Pd( ii ) and Pt( ii ) complexes [ML][PF 6 ] 2 [L = L 1 , M = Ni ( 1 ), Pd ( 2 ), Pt ( 3 ); L = L 2 , M = Ni ( 4 ), Pd ( 5 ), Pt ( 6 )] and [Pt(L 2 )(acac)] ( 7 ) have been prepared by the reactions of two tetradentate macrocyclic amine-NHC ligand precursors, [H 2 L 1 ][PF 6 ] 2 and [H 2 L 2 ][PF 6 ] 2 , with Ni(OAc) 2 ·4H 2 O, Pd(OAc) 2 and Pt(acac) 2 in the presence of NaOAc. Complex 7 is isolated along with 6 from the same reaction between [H 2 L 2 ][PF 6 ] 2 and Pt(acac) 2 . There are two atropisomers in 1–3 and two achiral conformers in 4–6 . The crystal structures of 1–3 and one conformer of 4–6 ( 4a–6a ) have been determined by single-crystal X-ray diffraction studies. The metal ion is found to reside in the cavity of the macrocyclic ring and adopts a square-planar configuration. Detailed NMR studies including variable-temperature NMR spectroscopy reveal a dynamic interconverting process between two atropisomers of 1–3 in the solutions via a ring twisting mechanism. Two conformers in the equilibrated solution of 4–6 , probably arising from the orientation of two amine N–H bonds with respect to the coordination plane, exchange slowly. Time-dependent 1 H NMR spectra show that one conformer ( 4a–6a ) in solution converts into the other ( 4b–6b ) via the inversion of the nitrogen atom. 
    more » « less
  3. ; ; ; (, IUCrData)
    Crystals of the title salt, (C8H20N)[Sn(C6H5)3(C2H2O2S)], comprise diisobutylammonium cations and mercaptoacetatotriphenylstannate(IV) anions. The bidentate binding mode of the mercaptoacetate ligand gives rise to a five-coordinated, ionic triphenyltin complex with a distortedcis-trigonal–bipyramidal geometry around the tin atom. In the crystal, charge-assisted ammonium-N—H...O(carboxylate) hydrogen-bonding connects two cations and two anions into a four-ion aggregate. Two positions were resolved for one of the phenyl rings with the major component having a site occupancy factor of 0.60 (3). 
    more » « less
  4. ; ; ; (, Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials)
    The results of the structural determination, magnetic characterization, and theoretical calculations of a new ruthenium-oxo complex, Li 4 [Ru 2 OCl 10 ]·10H 2 O, are presented. Single crystals were grown using solvent methods and the crystal structure was characterized by single crystal X-ray diffraction. Li 4 [Ru 2 OCl 10 ]·10H 2 O crystallizes into a low-symmetry triclinic structure ( P 1 ) due to the much smaller Li + cation compared to K + cation in the tetragonal complex K 4 [Ru 2 OCl 10 ]·H 2 O. The X-ray photoelectron spectra confirm only the single valent Ru 4+ in Li 4 [Ru 2 OCl 10 ]·10H 2 O even though two distinct Ru sites exist in the crystal structure. Magnetic measurements reveal the diamagnetic property of Li 4 [Ru 2 OCl 10 ]·10H 2 O with unpaired electrons existing on Ru 4+ . Furthermore, the molecular orbital analysis matches well with the observed UV and magnetic measurements. 
    more » « less
  5. ; ; ; ; ; ; ; (, Acta Crystallographica Section E Crystallographic Communications)
    Structural analyses of the compounds di-μ-acetato-κ 4 O : O ′-bis{[2-methoxy- N , N -bis(quinolin-2-ylmethyl)ethanamine-κ 4 N , N ′, N ′′, O ]manganese(II)} bis(tetraphenylborate) dichloromethane 1.45-solvate, [Mn 2 (C 23 O 2 ) 2 (C 23 H 23 N 3 O) 2 ](C 24 H 20 B)·1.45CH 2 Cl 2 or [Mn(DQMEA)(μ-OAc) 2 Mn(DQMEA)](BPh 4 ) 2 ·1.45CH 2 Cl 2 or [1] (BPh 4 ) 2 ·1.45CH 2 Cl 2 , and (acetato-κ O )[2-hydroxy- N , N -bis(quinolin-2-ylmethyl)ethanamine-κ 4 N , N ′, N ′′, O ](methanol-κ O )manganese(II) tetraphenylborate methanol monosolvate, [Mn(CH 3 COO)(C 22 H 21 N 3 O)(CH 3 OH)](C 24 H 20 B)·CH 3 OH or [Mn(DQEA)(OAc)(CH 3 OH)]BPh 4 ·CH 3 OH or [2] BPh 4 ·CH 3 OH, by single-crystal X-ray diffraction reveal distinct differences in the geometry of coordination of the tripodal DQEA and DQMEA ligands to Mn II ions. In the asymmetric unit, compound [1] (BPh 4 ) 2 ·(CH 2 Cl 2 ) 1.45 crystallizes as a dimer in which each manganese(II) center is coordinated by the central amine nitrogen, the nitrogen atom of each quinoline group, and the methoxy-oxygen of the tetradentate DQMEA ligand, and two bridging-acetate oxygen atoms. The symmetric Mn II centers have a distorted, octahedral geometry in which the quinoline nitrogen atoms are trans to each other resulting in co-planarity of the quinoline rings. For each Mn II center, a coordinated acetate oxygen participates in C—H...O hydrogen-bonding interactions with the two quinolyl moieties, further stabilizing the trans structure. Within the crystal, weak π – π stacking interactions and intermolecular cation–anion interactions stabilize the crystal packing. In the asymmetric unit, compound [2] BPh 4 ·CH 3 OH crystallizes as a monomer in which the manganese(II) ion is coordinated to the central nitrogen, the nitrogen atom of each quinoline group, and the alcohol oxygen of the tetradentate DQEA ligand, an oxygen atom of OAc, and the oxygen atom of a methanol ligand. The geometry of the Mn II center in [2] BPh 4 ·CH 3 OH is also a distorted octahedron, but the quinoline nitrogen atoms are cis to each other in this structure. Hydrogen bonding between the acetate oxygen atoms and hydroxyl (O—H...O) and quinolyl (C—H...O and N—H...O) moieties of the DQEA ligand stabilize the complex in this cis configuration. Within the crystal, dimerization of complexes occurs by the formation of a pair of intermolecular O3—H3...O2 hydrogen bonds between the coordinated hydroxyl oxygen of the DQEA ligand of one complex and an acetate oxygen of another. Additional hydrogen-bonding and intermolecular cation–anion interactions contribute to the crystal packing. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email