+ Site Statistics
References:
54,258,434
Abstracts:
29,560,870
PMIDs:
28,072,757
+ Search Articles
+ PDF Full Text Service
How our service works
Request PDF Full Text
+ Follow Us
Follow on Facebook
Follow on Twitter
Follow on LinkedIn
+ Subscribe to Site Feeds
Most Shared
PDF Full Text
+ Translate
+ Recently Requested

Compounds with the electron-rich [W6Cl18]2- cluster anion



Compounds with the electron-rich [W6Cl18]2- cluster anion



Inorganic Chemistry 48(8): 3825-3831



Cluster compounds of the general formula A(2)[W(6)Cl(18)] containing singly charged A cations (A = K, Rb, Ag, Tl, NH(4), N(C(2)H(5))(4), N(n-C(3)N(7))(4), N(n-C(4)H(9))(4)) and [W(6)Cl(18)](2-) anions have been synthesized. Compounds were obtained by W(6)Cl(18) reduction using methanol and the corresponding metal or (alkyl-)ammonium salts. The use of CoCp(2) as reducing agent in inert solvents such as tetrahydrofurane also leads to the ionic compound (Co(C(5)H(5))(2))(2)[W(6)Cl(18)]. All compounds described here evidence the existence of octahedral clusters of the M(6)X(12) type with 20 cluster electrons occupying metal centered states, thus exceeding the conventional number of 16 electrons for this cluster type. Electrospray ionization (ESI) mass spectra were recorded for the neutral compound W(6)Cl(18) and for the ionic salts K(2)[W(6)Cl(18)], Cs(2)[W(6)Cl(18)], and (Co(C(5)H(5))(2))(2)[W(6)Cl(18)], showing that the cluster W(6)Cl(18) unit in these compounds is preserved in solution. The base peak in the ESI spectra for all compounds corresponds to the [W(6)Cl(18)](2-) anion, so that neutral W(6)Cl(18) is prone to undergo a two electron reduction process. This result is confirmed by cyclic voltammetry experiments, which makes of W(6)Cl(18) a very clean mild oxidizing agent. The preparation of the complete series of ionic A(2)[W(6)Cl(18)] (A = K, Cs, CoCp(2)) clusters allows to systematically investigate their structural trends as function of the distinctive cations, which is the main focus of the present work.

Please choose payment method:






(PDF emailed within 0-6 h: $19.90)

Accession: 052269460

Download citation: RISBibTeXText

PMID: 19361250

DOI: 10.1021/ic8019843


Related references

Electron exchange between alpha-Keggin tungstoaluminates and a well-defined cluster-anion probe for studies in electron transfer. Inorganic Chemistry 44(24): 8955-8966, 2005

Rotational Cluster Anion Enabling Superionic Conductivity in Sodium-Rich Antiperovskite Na 3 OBH 4. Journal of the American Chemical Society 2019, 2019

Electron transfer mechanisms for the photoassisted decomposition of electron rich and electron poor aromatic compounds in aqueous solution. Abstracts of Papers American Chemical Society 203(1-3): ENVR138, 1992

The [(AL2O3)2]- anion cluster: electron localization-delocalization isomerism. Chemphyschem 10(14): 2410-2413, 2009

Al4- cluster anion: electronic structure, excited states, and electron detachment. Journal of Chemical Physics 132(12): 124305, 2010

Hydrolysis of tosyl esters initiated by an electron transfer from photoexcited electron rich aromatic compounds. Journal of Organic Chemistry 53(14): 3386-3387, 1988

A new class of electron-rich unsaturated molecules: Ru2HnX4-n(PiPr3)4, X = anion. Inorganic Chemistry 39(17): 3757-3764, 2001

Electrochemical addition of chlorodifluoroacetyl aromatic compounds to electron-rich olefinic substrates A convenient synthesis of gem-difluoro heterocyclic compounds. Tetrahedron Letters 36(12): 2071-2074, 1995

Electron Spin Manipulation via Encaged Cluster: Differing Anion Radicals of Y2@C82-Cs, Y2C2@C82-Cs, and Sc2C2@C82-Cs. Journal of Physical Chemistry Letters 4(3): 464-467, 2013

Neither electron-precise nor in accordance with Wade-Mingos rules: the ternary cluster anion [Ni2Sn7Bi5]3-. Angewandte Chemie 50(4): 955-959, 2011

Imidometallanes and their heavy analogs: rich gas phase chemistry of ring and cluster compounds. Inorganic Chemistry Communications 6(3): 274-277, 2003

Orbital effect-induced anomalous anion-π interactions between electron-rich aromatic hydrocarbons and fluoride. Chemphyschem 15(12): 2588-2594, 2014

Organic styryl quinolinium crystal with aromatic anion bearing electron-rich vinyl group. Journal of Molecular Structure 1100: 359-365, 2015

The magnetic behaviour of [NnBu4]4[Ni16Pd16(CO)40]: an even-electron homoleptic carbonyl-metal cluster anion displaying a J = 2 ground state. Chemistry 11(9): 2856-2861, 2005

Cycloaddition reaction of 2-azadienes derived from beta-amino acids with electron-rich and electron-deficient alkenes and carbonyl compounds. Synthesis of pyridine and 1,3-oxazine derivatives. Journal of Organic Chemistry 67(7): 2131-2135, 2002