Header

UZH-Logo

Maintenance Infos

Coordination Properties of Multidentate Phosphanylborane Ligands in Tungsten Nitrosyl Complexes


Jana, R; Blacque, O; Jiang, Y; Berke, H (2013). Coordination Properties of Multidentate Phosphanylborane Ligands in Tungsten Nitrosyl Complexes. European Journal of Inorganic Chemistry, 2013(18):3155-3166.

Abstract

The ambiphilic and small-bite-angle diphosphanylborane ligands Ph2PCH(PPh2)CH2B(C8H14) (2) and Ph2PCH2CH[B(C8H14)]PPh2 (3) containing the Lewis acidic 9-boranorbornyl group B(C8H14) have been prepared in one step by regioselective anti-Markovnikov hydroborations of 1,1-bis(diphenylphosphanyl)ethylene and 1,2-bis(diphenylphosphanyl)ethylene with 9-borabicyclo[3.3.1]nonane (9-BBN) under relatively drastic reaction condition. The coordination properties of Ph2PCH2CH2B(C8H14) (1) and the newly prepared 2 and 3 towards the tungsten nitrosyl fragment {WNO}6 have been studied structurally and spectroscopically. Herein, we report the cis and trans tungsten nitrosyl complexes cis-[W(CO)2(1)2(NO)(Cl)] (cis-4a), cis-[W(CO)2(1)2(NO)(H)] (cis-4b), trans-[W(CO)2(1)2(NO)(Cl)] (trans-4a), trans-[W(CO)2(1)2(NO)(H)] (trans-4b), cis-[W(CO)2(2)(NO)(Cl)] (cis-5a), cis-[W(CO)2(2)(NO)(H)] (cis-5b), cis-[W(CO)2(3)(NO)(Cl)] (cis-6a), cis-[W(CO)2(3)(NO)(H)] (cis-6b), which were readily obtained from straightforward ligand-substitution reactions of the tungsten carbonyl nitrosyl precursor [W(NO)(CO)4(ClAlCl3)] in tetrahydrofuran. The crystal structures of the tungsten chloride complexes cis-4a, trans-4a, and cis-5a revealed that the trialkyl boron centers are free pendants in the secondary coordination spheres, whereas in the hydride complexes trans-4b, cis-5b, and cis-6b the hydride ligand trans to the nitrosyl ligand is σ coordinated to the tethered B(C8H14) group and form three-center, two-electron (3c–2e) W–H–B bonds, which were observed in their crystal structures. The authenticity of the 3c–2e W–H–B bond in the tungsten hydride complex cis-5b was further checked by a DFT structural optimization and natural bond order (NBO) analysis.

Abstract

The ambiphilic and small-bite-angle diphosphanylborane ligands Ph2PCH(PPh2)CH2B(C8H14) (2) and Ph2PCH2CH[B(C8H14)]PPh2 (3) containing the Lewis acidic 9-boranorbornyl group B(C8H14) have been prepared in one step by regioselective anti-Markovnikov hydroborations of 1,1-bis(diphenylphosphanyl)ethylene and 1,2-bis(diphenylphosphanyl)ethylene with 9-borabicyclo[3.3.1]nonane (9-BBN) under relatively drastic reaction condition. The coordination properties of Ph2PCH2CH2B(C8H14) (1) and the newly prepared 2 and 3 towards the tungsten nitrosyl fragment {WNO}6 have been studied structurally and spectroscopically. Herein, we report the cis and trans tungsten nitrosyl complexes cis-[W(CO)2(1)2(NO)(Cl)] (cis-4a), cis-[W(CO)2(1)2(NO)(H)] (cis-4b), trans-[W(CO)2(1)2(NO)(Cl)] (trans-4a), trans-[W(CO)2(1)2(NO)(H)] (trans-4b), cis-[W(CO)2(2)(NO)(Cl)] (cis-5a), cis-[W(CO)2(2)(NO)(H)] (cis-5b), cis-[W(CO)2(3)(NO)(Cl)] (cis-6a), cis-[W(CO)2(3)(NO)(H)] (cis-6b), which were readily obtained from straightforward ligand-substitution reactions of the tungsten carbonyl nitrosyl precursor [W(NO)(CO)4(ClAlCl3)] in tetrahydrofuran. The crystal structures of the tungsten chloride complexes cis-4a, trans-4a, and cis-5a revealed that the trialkyl boron centers are free pendants in the secondary coordination spheres, whereas in the hydride complexes trans-4b, cis-5b, and cis-6b the hydride ligand trans to the nitrosyl ligand is σ coordinated to the tethered B(C8H14) group and form three-center, two-electron (3c–2e) W–H–B bonds, which were observed in their crystal structures. The authenticity of the 3c–2e W–H–B bond in the tungsten hydride complex cis-5b was further checked by a DFT structural optimization and natural bond order (NBO) analysis.

Statistics

Citations

7 citations in Web of Science®
5 citations in Scopus®
Google Scholar™

Altmetrics

Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2013
Deposited On:07 Feb 2014 15:33
Last Modified:05 Apr 2016 17:30
Publisher:Wiley-Blackwell
ISSN:1434-1948
Publisher DOI:https://doi.org/10.1002/ejic.201201565

Download

Full text not available from this repository.
View at publisher

TrendTerms

TrendTerms displays relevant terms of the abstract of this publication and related documents on a map. The terms and their relations were extracted from ZORA using word statistics. Their timelines are taken from ZORA as well. The bubble size of a term is proportional to the number of documents where the term occurs. Red, orange, yellow and green colors are used for terms that occur in the current document; red indicates high interlinkedness of a term with other terms, orange, yellow and green decreasing interlinkedness. Blue is used for terms that have a relation with the terms in this document, but occur in other documents.
You can navigate and zoom the map. Mouse-hovering a term displays its timeline, clicking it yields the associated documents.

Author Collaborations