Trinuclear Mixed-valent Gold Complexes Derived from 2-C6F4PPh2: Phosphine Oxide Complexes of Gold(III) and an ortho-Metallated Complex of Gold(I)

2009 ◽  
Vol 64 (11-12) ◽  
pp. 1463-1468 ◽  
Author(s):  
Martin A. Bennett ◽  
Nedaossadat Mirzadeh ◽  
Steven H. Privér ◽  
Jörg Wagler ◽  
Suresh K. Bhargava
Keyword(s):  
Carbon Atom ◽  
Silver Nitrate ◽  
Phosphine Oxide ◽  
Phosphorus Atom ◽  
Phenyl Group ◽  
Large Excess ◽  
Gold Complexes ◽  
Nitrate Ion ◽  
Metal Atoms

Crystals of two mixed-valent gold complexes [(O2NO)AuI(μ-2-C6F4PPh2)AuIII{κ2-2-C6- F4P(O)Ph2}(μ-2-C6F4PPh2)AuI(ONO2)] (14) and [(O2NO)AuI(μ-2-C6F4PPh2)AuIII{κ3-2-C6F4- P(O)Ph(C6H4)}(μ-2-C6F4PPh2)AuI] (15) have been obtained from the reaction of the digold(I,III) complex [ClAuI(μ-2-C6F4PPh2)(κ2-2-C6F4PPh2)AuIIICl] (5) with, respectively, a small and a large excess of silver nitrate. Both complexes contain three, approximately collinear metal atoms, the central gold(III) atom being planar-coordinated by a chelate (O,C)-phosphine oxide formed by oxidation of 2-C6F4PPh2 and the carbon atoms of two bridging 2-C6F4PPh2 groups. In 14 each of the terminal gold(I) atoms is coordinated by a monodentate nitrate ion and the phosphorus atom of μ-2-C6F4PPh2, whereas in 15 the nitrate ion on one of the gold(I) atoms of 14 has been replaced by the carbon atom of a bridging C6H4 group derived by Ag+-promoted cyclometallation of a phenyl group on the neighbouring phosphine oxide

scholarly journals A soft phosphorus atom to “harden” an erbium(iii) single-ion magnet

2018 ◽  
Vol 9 (38) ◽  
pp. 7540-7545 ◽  
Author(s):  
Shi-Ming Chen ◽  
Jin Xiong ◽  
Yi-Quan Zhang ◽  
Qiong Yuan ◽  
Bing-Wu Wang ◽  
...  
Keyword(s):  
Carbon Atom ◽  
Phosphorus Atom ◽  
Blocking Temperature

A single-ion magnet (Dsp)Er(COT) was obtained by replacing a carbon atom of [Cp*]− in (Cp*)Er(COT) by a soft P atom. Both relaxation barrier and blocking temperature are improved.

Coordination chemistry of gold with N-phosphine oxide-substituted imidazolylidenes (POxIms)

2019 ◽  
Vol 43 (44) ◽  
pp. 17275-17283 ◽  
Author(s):  
Lorenzo Branzi ◽  
Marco Baron ◽  
Lidia Armelao ◽  
Marzio Rancan ◽  
Paolo Sgarbossa ◽  
...  
Keyword(s):  
Coordination Chemistry ◽  
Phosphine Oxide ◽  
Structural Features ◽  
Gold Complexes ◽  
Catalytic Performances

Diverse gold complexes are found to be accessible with the title ligands, which exhibit peculiar structural features and promising catalytic performances.

Orientation of phenyl group attached to phosphorus atom in 5-phenyl-1,3-di-R-1,3,5-diazaphosphorinanes

1980 ◽  
Vol 29 (7) ◽  
pp. 1115-1119 ◽  
Author(s):  
B. A. Arbuzov ◽  
O. A. Erastov ◽  
G. N. Nikonov ◽  
T. A. Zyablikova ◽  
R. P. Arshinova ◽  
...  
Keyword(s):  
Phosphorus Atom ◽  
Phenyl Group

Silver and Gold Complexes with Benzimidazolin-2-ylidene Ligands

2009 ◽  
Vol 64 (11-12) ◽  
pp. 1458-1462 ◽  
Author(s):  
Mareike C. Jahnke ◽  
Jennifer Paley ◽  
Florian Hupka ◽  
Jan J. Weigand ◽  
F. Ekkehardt Hahn
Keyword(s):  
Carbon Atom ◽  
Silver Oxide ◽  
Silver Complexes ◽  
X Ray Diffraction ◽  
Gold Complexes ◽  
X Ray ◽  
Linear Fashion ◽  
Diffraction Structure ◽  
Benzimidazolium Salts

The dicarbene silver complexes 1a, b of the type [Ag(NHC)2][AgBr2] (NHC = N,N'-dialkylbenzimidazolin- 2-ylidene) have been prepared from the parent benzimidazolium salts by reaction with silver oxide. The silver complexes have been used for the transfer of the carbene ligand to gold(I) giving the gold complexes [AuCl(NHC)] 2a, b in good yields. Crystals of 2a, b have been obtained from chloroform/pentane solutions, and X-ray diffraction structure analyses revealed gold(I) atoms coordinated in a linear fashion by an NHC carbon atom and a chloro ligand

scholarly journals A Boron-Transfer Mechanism Mediating the Thermally Induced Revival of Frustrated Carbene−Borane Pairs from their Shelf-Stable Adducts

2021 ◽  
Author(s):  
Yoichi Hoshimoto ◽  
Mahiro Sakuraba ◽  
Takuya Kinoshita ◽  
Masaki Ohbo ◽  
Manussada Ratanasak ◽  
...  
Keyword(s):  
Reaction Mechanism ◽  
Carbon Atom ◽  
Oxygen Atom ◽  
Phosphine Oxide ◽  
Theoretical Studies ◽  
Stimuli Responsive ◽  
Thermally Induced ◽  
Shelf Stable ◽  
External Stimuli ◽  
Experimental And Theoretical Studies

Combined experimental and theoretical studies allowed clarifying the reaction mechanism for the revival of frustrated carbene−borane pairs from external-stimuli-responsive classical Lewis adducts comprised of N-phosphine oxide-substituted imidazolylidenes and triarylboranes. A borane-transfer process from the carbene carbon atom to the N-phosphinoyl oxygen atom was identified as the rate-determining event for the regeneration of the FLP species, eventually enabling the heterolytic cleavage of H2.<br>

Zur Stereochemie der Phosphinoxydspaltung von R-(+)-Methyl-phenyl-α -naphthyl-allyl-phosphoniumbromid / The Stereochemistry of the Phosphine Oxide Cleavage of R-(+)-Methyl-phenyl-α-naphthyl-allyl-phosphonium Bromide

1975 ◽  
Vol 30 (1-2) ◽  
pp. 119-123 ◽  
Author(s):  
Reiner Luckenbach
Keyword(s):  
Phosphine Oxide ◽  
Phosphorus Atom ◽  
Phosphonium Bromide ◽  
Methyl Phenyl

The stereochemical course of the ‘phosphine oxide cleavage’ of chiral R-(+)-methylphenyl-α-naphthyl-allyl-phosphonium bromide is reported. While the α-naphthyl group is cleaved by alkali with predominant retention of configuration at the central phosphorus atom, the allyl group is split off with predominant inversion.

ChemInform Abstract: CYCLIC COMPOUNDS WITH A FIVE-COORDINATE PHOSPHORUS ATOM - BIS(O-TOLYL)PHOSPHINE OXIDE DERIVATIVES

1978 ◽  
Vol 9 (22) ◽  
Author(s):  
K. A. PETROV ◽  
V. A. CHAUZOV ◽  
N. YU. MAL'KEVICH ◽  
S. M. KOSTROVA
Keyword(s):  
Phosphine Oxide ◽  
Phosphorus Atom ◽  
Cyclic Compounds

Matter Falling Out: Precipitation

Reactions ◽  
2011 ◽  
Author(s):  
Peter Atkins
Keyword(s):  
Sodium Chloride ◽  
Silver Nitrate ◽  
Weak Interactions ◽  
Silver Chloride ◽  
Nitrate Solution ◽  
Chloride Ion ◽  
Silver Nitrate Solution ◽  
Common Salt ◽  
Nitrate Ion ◽  
To Come

I shall now introduce you to one of the simplest kinds of chemical reaction: precipitation, the falling out from solution of newly formed solid, powdery matter when two solutions are mixed together. The process is really very simple and, I have to admit, not very interesting. However, I am treating it as your first encounter with creating a different form of matter from two starting materials, so please be patient as there are much more interesting processes to come. I would like you to regard it as a warming-up exercise for thinking about and visualizing chemical reactions at a molecular level. Not much is going on, so the steps of the reaction are reasonably easy to follow. There isn’t much to do to bring about a precipitation reaction. Two soluble substances are dissolved in water, one solution is poured into the other, and—providing the starting materials are well chosen—an insoluble powdery solid immediately forms and makes the solution cloudy. For instance, a white precipitate of insoluble silver chloride, looking a bit like curdled milk, is formed when a solution of sodium chloride (common salt) is poured into a solution of silver nitrate. Now, as we shall do many times in this book, let’s imagine shrinking to the size of a molecule and watch what happens when the sodium chloride solution is poured into the silver nitrate solution. As you saw in my Preliminary remark, when solid sodium chloride dissolves in water, Na+ ions and Cl– ions are seduced by water molecules into leaving the crystals of the original solid and spreading through the solution. Silver nitrate is AgNO3; Ag denotes a silver atom, which is present as the positive ion Ag+; NO3– is a negatively charged ‘nitrate ion’, 1. Silver nitrate is soluble because the negative charge of the nitrate ion is spread over its four atoms rather than concentrated on one, 2, as it is for the chloride ion, and as a result it has rather weak interactions with the neighbouring Ag+ ions in the solid.

Phosphonium salts. I. The alkaline hydrolysis of some bis-phosphonium salts

1969 ◽  
Vol 22 (7) ◽  
pp. 1385 ◽  
Author(s):  
JJ Brophy ◽  
MJ Gallagher
Keyword(s):  
Kinetic Study ◽  
Phosphine Oxide ◽  
Alkaline Hydrolysis ◽  
Phosphorus Atom ◽  
Phosphonium Salt ◽  
P System ◽  
Phosphonium Salts ◽  
Partial Explanation ◽  
Reaction Proceeds ◽  
Hydrolysis Of

Ethane- and ethene-1,2-bisphosphonium salts are cleaved by alkali into a phosphine and a phosphine oxide with loss of the two-carbon bridge. When the phosphorus atom carries benzyl substituents, loss of the benzyl groups is competitive with loss of the bridge. ��� Based on a kinetic study, a synchronous mechanism, analogous to the alkaline hydrolysis of acyclic monophosphonium salts, is proposed to account for the fragmentation. ��� With 6-membered 1,4-diphosphonio heterocyclic salts the nature of the products is dependent on whether alkali or phosphonium salt is present in excess. With an excess of alkali a synchronous mechanism again appears to operate, while with an excess of salt the reaction proceeds stepwise and without loss of the bridge. A partial explanation of these facts is advanced in terms of non-bonded interactions in the intermediate phosphoranes. ��� The synchronous reaction appears to be favoured by coplanarity of the P-C-C-P system.

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