Related Experiment Video

Updated: Feb 28, 2026

Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers

Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers

Published on: May 12, 2023

Preparation and Structure of Two Ditungsten Compounds Synthesized with the 3,5-Dichlorophenylformamidinate Ligand

Kathryn M. Carlson-Day¹, Judith L. Eglin, Laura T. Smith

¹Department of Chemistry, Harvard University, Cambridge, Massachusetts 02138.

Inorganic Chemistry

|October 24, 2001

Abstract:

The structure, preparation, and spectroscopy of a W(2)(II, II) paddlewheel complex with four formamidinate ligands is reported. Upon exposure to air and moisture in solution, the W(2)(II, II) core undergoes an oxidative addition reaction to form a W(2)(III, III) edge-sharing bioctahedral (ESBO) complex with two bridging hydroxides. The products, W(2)(&mgr;-DCPF)(4) (1) and W(2)(&mgr;-OH)(2)(&mgr;-DCPF)(2)(eta(2)-DCPF)(2) (2) where DCPF is [(3,5-Cl(2)C(6)H(3))NC(H)N(3,5-Cl(2)C(6)H(3))(-)], were characterized by UV-vis and (1)H NMR spectroscopy. Structural data are presented for W(2)(&mgr;-DCPF)(4) with four bridging formamidinate ligands and W(2)(&mgr;-OH)(2)(&mgr;-DCPF)(2)(eta(2)-DCPF)(2) with the formamidinate ligands in both chelating and bridging positions. Crystallographic data for W(2)(&mgr;-DCPF)(4) (1) and W(2)(&mgr;-OH)(2)(&mgr;-DCPF)(2)(eta(2)-DCPF)(2) (2) are as follows: (1), C(68)H(60)Cl(16)N(8)O(4)W(2), a = 12.6906(3) Å, b = 12.7818(4) Å, c = 13.0450(3) Å, alpha = 109.173(1) degrees, beta = 93.865(1) degrees, gamma = 103.746(1) degrees, triclinic, P&onemacr; (No. 2), and Z = 1 and (2), C(59)H(35)Cl(16)N(8)O(2)W(2), a = 17.1524(1) Å, b = 20.6568(3) Å, c = 19.3959(3) Å, beta = 102.791(1) degrees, monoclinic, C2/c (No. 15), and Z = 4.

More Related Videos

Scale-up Chemical Synthesis of Thermally-activated Delayed Fluorescence Emitters Based on the Dibenzothiophene-S,S-Dioxide Core

Scale-up Chemical Synthesis of Thermally-activated Delayed Fluorescence Emitters Based on the Dibenzothiophene-S,S-Dioxide Core

Published on: October 24, 2017

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI

Published on: November 22, 2016

Related Concept Videos

Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions

Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions

Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...

Diazonium Group Substitution: –OH and –H

Diazonium Group Substitution: –OH and –H

Nitrous acid, a weak acid, is prepared in situ via the reaction of sodium nitrite with a strong acid under cold conditions. This nitrous acid prepared in situ reacts with primary arylamines to form arenediazonium salts. Such reactions are known as diazotization reactions. As shown in Figure 1, the formation of arenediazonium salts begins with the decomposition of nitrous acid in an acidic solution to give nitrosonium ions.

Preparation of 1° Amines: Hofmann and Curtius Rearrangement Overview

Preparation of 1° Amines: Hofmann and Curtius Rearrangement Overview

In the presence of an aqueous base and a halogen, primary amides can lose the carbonyl (as carbon dioxide) and undergo rearrangement to form primary amines. This reaction, called the Hofmann rearrangement, can produce primary amines (aryl and alkyl) in high yields without contamination by secondary and tertiary amines.

Preparation of Acid Anhydrides

Preparation of Acid Anhydrides

One of the methods for preparing symmetrical or unsymmetrical acid anhydrides involves the treatment of acid chlorides with the sodium salt of carboxylic acids. The reaction proceeds via a nucleophilic acyl substitution.
The carboxylate ion acts as a nucleophile that attacks the carbonyl carbon of the acid chloride to form a tetrahedral intermediate. Subsequently, the re-formation of the carbonyl group with the loss of the chloride ion as a leaving group leads to the formation of an acid...

Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene

Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene

Bromination and chlorination of aromatic rings by electrophilic aromatic substitution reactions are easily achieved, but fluorination and iodination are difficult to achieve. Fluorine is so reactive that its reaction with benzene is difficult to control, resulting in poor yields of monofluoroaromatic products. To address this, Selectfluor reagent is used as a fluorine source in which a fluorine atom is bonded to a positively charged nitrogen.

Valence Bond Theory

Valence Bond Theory

Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...

Articles linked to this work by shared authors, journal, and citation graph.

Monomeric, Four-Coordinate Group 4 Metal Complexes with Chelating Bis(tert-butylamido)cyclodisilazane Ligands: Syntheses and Molecular Structures of {(MeSiN(t)Bu)(2)(N(t)Bu)(2)}MCl(2) and {(MeSiN(t)Bu)(2)(N(t)Bu)(2)}MMe(2), M = Zr, Hf.

Inorganic chemistry·2001

Heteroatom Derivatives of Cyclopentadienylaluminum: X-ray Crystal Structure of (eta(5)-C(5)H(5))(2,6-t-Bu-4-Me-C(6)H(2)O)(2)Al.

Inorganic chemistry·2001

Syntheses and Structural Characterization of Tetrahedral Four-Coordinate Gold(I) Complexes of 1,3,5-Triaza-7-phosphaadamantane. An Example of a Hydrogen-Bond-Directed Supramolecular Assembly.

Inorganic chemistry·1996

See all related articles