Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Tris(tetramethylguanidinyl)phosphine: The Simplest Non-ionic Phosphorus Superbase and Strongly Donating Phosphine Ligand.

ABSTRACT: We report the synthesis and properties of the much sought-after tris(1,1,3,3-tetramethylguanidinyl) phosphine P(tmg)₃ , a crystalline, superbasic phosphine accessible through a short and scalable procedure from the cheap and commercially available bulk chemicals 1,1,3,3-tetramethylguanidine, tris(dimethylamino)-phosphine and phosphorus trichloride. The new phosphine exhibits exceptional electron donor properties and readily forms transition metal complexes with gold(I), palladium(II) and rhodium(I) precursors. The formation of zwitterionic Lewis base adducts with carbon dioxide and sulfur dioxide was explored. In addition, the complete series of phosphine chalcogenides was prepared from the reaction of P(tmg)₃ with N₂ O and the elemental chalcogens.

SUBMITTER: Buß F

PROVIDER: S-EPMC9300019 | biostudies-literature | 2022 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Tris(tetramethylguanidinyl)phosphine: The Simplest Non-ionic Phosphorus Superbase and Strongly Donating Phosphine Ligand.

Buß Florenz F Röthel Maike B MB Werra Janina A JA Rotering Philipp P Wilm Lukas F B LFB Daniliuc Constantin G CG Löwe Pawel P Dielmann Fabian F

Chemistry (Weinheim an der Bergstrasse, Germany) 20211209 3

We report the synthesis and properties of the much sought-after tris(1,1,3,3-tetramethylguanidinyl) phosphine P(tmg)<sub>3</sub> , a crystalline, superbasic phosphine accessible through a short and scalable procedure from the cheap and commercially available bulk chemicals 1,1,3,3-tetramethylguanidine, tris(dimethylamino)-phosphine and phosphorus trichloride. The new phosphine exhibits exceptional electron donor properties and readily forms transition metal complexes with gold(I), palladium(II) ...[more]

PMID: 34793627

Similar Datasets

Sterically Crowded Tris(2-(trimethylsilyl)phenyl)phosphine - Is it Still a Ligand?

Project description:Tris(2-(trimethylsilyl)phenyl)phosphine, P(o-TMSC6 H4 )3 , was synthesised and characterised in solution and in the solid state. The large steric bulk prevents most reactions of the phosphorus donor and makes the compound air stable both in the solid state as well as in solution. This shielded phosphine can still undergo three reactions, namely protonation, oxidation to the phosphine oxide under harsh conditions and complexation to AuI , thus forming a complex with linear coordination. Unexpectedly, complexation was unsuccessful with a range of other metal cations. Neither PdII , PtII , ZnII nor HgII reacted and even the remaining coinage metal cations CuI and AgI could not be coordinated. Both the parent molecule as well as the reaction products were structurally characterised by single crystal X-ray diffraction, and the conformational change of geometry required to accommodate the additional atoms was analysed in detail. Apart from chemical oxidation with H2 O2 , P(o-TMSC6 H4 )3 displays reversible electrochemical oxidation with a potential not unlike the one of sterically unencumbered phosphines for which the oxidation is usually not reversible. P(o-TMSC6 H4 )3 can thus be considered a model compound for the investigation of the electronic properties of sterically unencumbered phosphines.

| S-EPMC9303349 | biostudies-literature

Tris(2-methoxy-phen-yl)phosphine.

Project description:In the title compound, C(21)H(21)O(3)P, the whole mol-ecule is disordered over two sets of positions with refined occupancies of 0.503 (1) and 0.497 (1). The dihedral angles between the three benzene rings are 72.9 (2)°, 82.9 (3)° and 70.0 (2)° in the major disorder component and the corresponding angles in the minor disorder component are 85.0 (2)°, 79.2 (2)° and 72.3 (2)°. The crystal structure is stabilized by C-H⋯π inter-actions.

| S-EPMC2969262 | biostudies-literature

Cyanidophenyl-tris(trimethyl-phosphine)cobalt(II).

Project description:The title mol-ecule, [Co(C(6)H(5))(CN)(C(3)H(9)P)(3)], lies on a crystallographic mirror plane with the Co(II) ion coordinated in a distorted square-pyramidal environment with one of the P atoms in the apical position. In the basal plane, the phenyl substituent is trans to the cyanide group with a C-Co-C angle which is significantly distorted from linearity.

| S-EPMC2915065 | biostudies-literature

Tris(thio-cyanato-κN)tris-(triphenyl-phosphine oxide-κO)terbium(III).

Project description:The title compound, [Tb(NCS)3(C18H15OP)3], contains a six-coordinate Tb(II) cation surrounded by three O-bound triphenyl-phosphine oxide ligands and three N-bound thio-cyanate ligands, each in a fac arrangement. There are two crystallographically unique Tb(III) atoms in the asymmetric unit. One Tb(III) atom resides on a threefold rotation axis, while the other has no imposed crystallographic symmetry. The thio-cyanate ligands are bound through N atoms, illustrating the hard-hard bonding principles of metal complex chemistry.

| S-EPMC3588775 | biostudies-literature

Rapid water oxidation electrocatalysis by a ruthenium complex of the tripodal ligand tris(2-pyridyl)phosphine oxide.

Project description:The tris(2-pyridyl)phosphine oxide (Py3PO) complex [Ru(Py3PO)(bpy)(OH2)]2+ (bpy is 2,2'-bipyridine) is a pH-dependent water oxidation electrocatalyst that accelerates dramatically with increasing pH-up to 780 s-1 at pH 10 (∼1 V overpotential). Despite retaining the pentakis(pyridine) ligand arrangement common to previously reported catalysts, the tripodal Py3PO ligand framework supports much faster electrocatalysis. The early stages of the catalytic cycle are proposed to follow the typical pattern of single-site ruthenium catalysts, with two sequential 1H+/1e- proton-coupled electron transfer (PCET) oxidations, but the pH-dependent onset of catalysis and rapid rates are distinguishing features of the present system.

| S-EPMC5488214 | biostudies-literature

Tris(4-methyl-phen-yl)phosphine selenide.

Project description:In the title mol-ecule, C(21)H(21)PSe or PSe(C(7)H(7))(3), the P atom has a distorted PSeC(3) tetra-hedral environment, formed by the Se atom [P=Se = 2.1119 (5) Å] and three aryl rings. Two short intra-molecular C-H⋯Se contacts occur. In the crystal, weak inter-molecular C-H⋯Se inter-actions link the mol-ecules into zigzag double chains propagating in [100]. The previous report of this structure [Zhdanov et al. (1953 ▶). Dokl. Akad. Nauk SSSR (Russ.) (Proc. Nat. Acad. Sci. USSR), 92, 983-985] contained no geometrical data.

| S-EPMC3050420 | biostudies-literature

Enhanced activity of hyperthermostable Pyrococcus horikoshii endoglucanase in superbase ionic liquids.

Project description:ObjectivesIonic liquids (ILs) that dissolve biomass are harmful to the enzymes that degrade lignocellulose. Enzyme hyperthermostability promotes a tolerance to ILs. Therefore, the limits of hyperthemophilic Pyrococcus horikoschii endoglucanase (PhEG) to tolerate 11 superbase ILs were explored.ResultsPhEG was found to be most tolerant to 1-ethyl-3-methylimidazolium acetate ([EMIM]OAc) in soluble 1% carboxymethylcellulose (CMC) and insoluble 1% Avicel substrates. At 35% concentration, this IL caused an increase in enzyme activity (up to 1.5-fold) with CMC. Several ILs were more enzyme inhibiting with insoluble Avicel than with soluble CMC. Km increased greatly in the presence ILs, indicating significant competitive inhibition. Increased hydrophobicity of the IL cation or anion was associated with the strongest enzyme inhibition and activation. Surprisingly, PhEG activity was increased 2.0-2.5-fold by several ILs in 4% substrate. Cations exerted the main role in competitive inhibition of the enzyme as revealed by their greater binding energy to the active site.ConclusionsThese results reveal new ways to design a beneficial combination of ILs and enzymes for the hydrolysis of lignocellulose, and the strong potential of PhEG in industrial, high substrate concentrations in aqueous IL solutions.

| S-EPMC9356960 | biostudies-literature

Preconcentration of Superbase Ionic Liquid from Aqueous Solution by Membrane Filtration

Project description:Certain organic superbase ionic liquids (ILs) have shown

| S-EPMC9777811 | biostudies-literature

(Perchlorato-κO)tris-(triphenyl-phosphine-κP)silver(I).

Project description:In the title complex, [Ag(C(18)H(15)P)(3)(ClO(4))], the silver coord-ination environment is dominated by the distorted P(3)AgO tetra-hedron in which Ag-O = 2.608 (12) Å and the Ag-P bond lengths are 2.5663 (17), 2.5076(16) and 2.5450 (17) Å. The perchlorate O-atoms are disordered over two positions in a 0.584 (14):0.416 (14) ratio.

| S-EPMC3007391 | biostudies-literature

(2,6-Difluoro-benzophenone)tris-(trimethyl-phosphine)cobalt(0).

Project description:In the title compound, [Co(C(13)H(8)F(2)O)(C(3)H(9)P)(3)], the cobalt(0) atom is coordinated by three trimethyl-phosphine ligands and a π-coordinated carbonyl group of the 2,6-difluoro-benzo-phenone ligand in a distorted tetra-hedral geometry. The Co-O and Co-C distances are 1.896 (2) and 2.049 (4) Å, respectively.

| S-EPMC2977559 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data