Neutral and cationic phosphine and arsine complexes of tin(iv) halides: synthesis, properties, structures and anion influence.

07:00 EST 8th November 2019 | BioPortfolio

Summary of "Neutral and cationic phosphine and arsine complexes of tin(iv) halides: synthesis, properties, structures and anion influence."

The reaction of trans-[SnCl4(PR3)2] (R = Me or Et) with trimethylsilyltriflate (TMSOTf) in CH2Cl2 solution substitutes one chloride to form [SnCl3(PR3)2(OTf)]; addition of excess TMSOTf does not substitute further chlorides. The complexes have been fully characterised by microanalysis, IR and multinuclear NMR (1H, 13C{1H}, 19F{1H}, 31P{1H}, 119Sn) spectroscopy. The crystal structure of [SnCl3(PMe3)2(OTf)] revealed mer-chlorines and trans-phosphines. In contrast, trans-[SnBr4(PR3)2], [SnCl4{Et2P(CH2)2PEt2}], [SnCl4{o-C6H4(PMe2)2}] and [SnCl4{o-C6H4(AsMe2)2}] did not react with TMSOTf in CH2Cl2 solution even after 3 days. The arsine complexes, [SnX4(AsEt3)2] (X = Cl, Br), were confirmed as trans-isomers by similar spectroscopic and structural studies, while attempts to isolate [SnI4(AsEt3)2] were unsuccessful and reaction of SnX4 with SbR3 (R = Et, iPr) resulted in reduction to SnX2 and formation of R3SbX2. trans-[SnCl4(AsEt3)2] is converted by TMSOTf into [SnCl3(AsEt3)2(OTf)], whose X-ray structure reveals the same geometry found in the phosphine analogues, with the triflate coordinated. The salts, [SnCl3(PEt3)2][AlCl4] and [SnCl2(PEt3)2][AlCl4]2 were made by treatment of [SnCl4(PEt3)2] with one and two mol. equivalents, respectively, of AlCl3 in anhydrous CH2Cl2, whereas reaction of [SnCl4(AsEt3)2] with AlCl3 produced a mixture including Et3AsCl2 and [Et3AsCl][Sn(AsEt3)Cl5] (the latter identified crystallographically). In contrast, using Na[BArF] (BArF = [B{3,5-(CF3)2C6H3}4]-) produced [SnCl3(PEt3)2][BArF] and also allowed clean isolation of the arsine analogue, [SnCl3(AsEt3)2][BArF]. [SnCl4{o-C6H4(PMe2)2}] also reacts with AlCl3 in CH2Cl2 to form [SnCl3{o-C6H4(PMe2)2}][AlCl4] and [SnCl2{o-C6H4(PMe2)2}][AlCl4]2. Multinuclear NMR spectroscopy on the [AlCl4]- salts show that δ31P and δ119Sn move progressively to high frequency on conversion from the neutral complex to the mono- and the di-cations, whilst 1J(119Sn-31P) follow the trend: [SnCl3{o-C6H4(PMe2)2}]+ > [SnCl4{o-C6H4(PMe2)2}] > [SnCl2{o-C6H4(PMe2)2}]2+. DFT studies on selected complexes show only small changes in ligand geometries and bond lengths between the halide and triflate complexes, consistent with the X-ray crystallographic data reported and the HOMO and LUMO energies are relatively unperturbed upon the introduction of (coordinated) triflate, whereas the energies of both are ca. 4 eV lower in the cationic species and reveal significant hybridisation across the pnictine ligands.


Journal Details

This article was published in the following journal.

Name: Dalton transactions (Cambridge, England : 2003)
ISSN: 1477-9234


DeepDyve research library

PubMed Articles [12205 Associated PubMed Articles listed on BioPortfolio]

Rapid synthesis and anti-proliferative properties of polyazamacrocycle-based bi- and tetra-gold(I) phosphine dithiocarbamate complexes.

A family of bimetallic and of tetrametallic phosphine-gold(I)-dithiocarbamate complexes were synthesized starting from cyclam and dimethylcyclam polyazamacrocycles respectively, along with their monom...

Phosphine-Catalyzed Activation of Alkylidenecyclopropanes: Rearrangement to Form Polysubstituted Furans and Dienones.

We report a phosphine-catalyzed ring opening of electron-deficient alkylidenecyclopropanes (ACPs) to generate allylic phosphonium zwitterions that resemble the well-studied phosphine-allene adducts bu...

Syntheses and Catalytic Hydrogenation Performance of Cationic Bis(phosphine) Cobalt(I) Diene and Arene Compounds.

Chloride abstraction from [(R,R)-(iPrDuPhos)Co(μ-Cl)]2 with NaBArF-4(BArF4 = B[(3,5-(CF3)2)C6H3]4) in the presence of dienes such as 1,5-cyclooctadiene (COD) or norbornadiene (NBD) yielded long sough...

Immunoreactivity changes of human serum albumin and alpha-1-microglobulin induced by their interaction with dendrimers.

Dendrimers are hyperbranched polymers for delivery of therapeutic genetic material to cancer cells. The fine tuning chemical modifications of dendrimers allow for the modification of the composition. ...

Solution Behavior of Beryllium Halides in Dimethylformamide.

The reactivity of beryllium compounds in ,-dimethylformamide (DMF) is fairly uncharted. However, as a versatile O-donor solvent, DMF enables reaction conditions that are inaccessible in solvents more ...

Clinical Trials [1839 Associated Clinical Trials listed on BioPortfolio]

Eosinophilic Cationic Protein as a Biomarker in Diagnosis of Acute Exacerbation of Chronic Obstructive Pulmonary Disease

Chronic obstructive pulmonary disease is a type of obstructive lung disease characterized by long-term breathing problems and poor airflow. It is changed to acute exacerbation of Chronic o...

Neuroimaging of Pavlovian Fear Conditioning Processes in Patients With Pathological Anxiety

The purpose of this study is to use functional magnetic resonance imaging to investigate how the human brain learns to form associations between neutral and emotional stimuli. The study is...

Z-Joint Changes in Low Back Pain Following Adjusting

The purpose of this continuation project is to use MRI to evaluate gapping of the zygapophysial (Z) joints following side-posture positioning and side-posture spinal adjusting in subjects ...

The Prognostic Significance of Premature Ventricular Complexes in Patients Without Structural Heart Disease

With this project the investigators aim to investigate whether premature ventricular complexes (PVC) have a prognostic significance in persons without structural heart disease. Further the...

A Study Evaluating the Effects of Lipid Lowering Treatment on Steroid Synthesis

Cholesterol is the precursor of glucocorticoids, mineralocorticoids and sex steroids. Both adrenal and non-adrenal (ovarian + testicular) all steroid hormones are primarily synthesized usi...

Medical and Biotech [MESH] Definitions

Neutral or negatively charged ligands bonded to metal cations or neutral atoms. The number of ligand atoms to which the metal center is directly bonded is the metal cation's coordination number, and this number is always greater than the regular valence or oxidation number of the metal. A coordination complex can be negative, neutral, or positively charged.

One of several basic proteins released from EOSINOPHIL cytoplasmic granules. Eosinophil cationic protein is a 21-kDa cytotoxic peptide with a pI of 10.9. Although eosinophil cationic protein is considered a member of the RNAse A superfamily of proteins, it has only limited RNAse activity.

Inorganic or organic compounds derived from phosphine (PH3) by the replacement of H atoms. (From Grant & Hackh's Chemical Dictionary, 5th ed)

A ceramidase subtype that is active at neutral pH. It is found at high levels within the SMALL INTESTINE and in the BRAIN.

Amino acid transporter systems capable of transporting neutral amino acids (AMINO ACIDS, NEUTRAL).

Quick Search

DeepDyve research library

Relevant Topic

Radiology is the branch of medicine that studies imaging of the body; X-ray (basic, angiography, barium swallows), ultrasound, MRI, CT and PET. These imaging techniques can be used to diagnose, but also to treat a range of conditions, by allowing visuali...

Searches Linking to this Article