Structural diversity of halocarbonyl molybdenum and tungsten PNP pincer complexes through ligand modifications† †Electronic supplementary information (ESI) available: Complete crystallographic data and technical details in CIF format for 5a, 5b·1.5CH2Cl2, 6a·CDCl3, 7a, 8a and 10. Atomic coordinates for all DFT optimized structures. CCDC 1478552–1478557. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6dt02251k Click here for additional data file. Click here for additional data file.

نویسندگان

  • Sara R. M. M. de Aguiar
  • Berthold Stöger
  • Ernst Pittenauer
  • Günter Allmaier
  • Luis F. Veiros
  • Karl Kirchner
چکیده

This work presents a comparative study of a series of halocarbonyl Mo(ii) and W(ii) complexes of the types [M(PNP)(CO)3X]X and [M(PNP)(CO)2X2] (M = Mo, W; X = I, Br), featuring PNP pincer ligands based on a 2,6-diaminopyridine scaffold. The complexes were prepared and fully characterized. The syntheses of these complexes were accomplished by treatment of [M(PNP)(CO)3] with stoichiometric amounts of I2 and Br2, respectively. The modification of the 2,6-diaminopyridine scaffold by introducing NMe and NPh instead of NH spacers with concomitant modification of the phosphine moieties changed the steric and electronic properties of the PNP ligand significantly. While in the case of NH linkers exclusively cationic seven-coordinate complexes of the type [M(PNP)(CO)3X](+) were obtained with NMe and NPh spacers neutral seven-coordinate complexes of the type [M(PNP)(CO)2X2] were afforded. In the case of the latter, when the reaction is performed in the presence of CO also [M(PNP)(CO)3X](+) complexes are formed which slowly lose CO to give [M(PNP)(CO)2X2]. The halocarbonyl tungsten chemistry parallels that of molybdenum. The only exception is molybdenum in conjunction with the PNP(Me)-iPr ligand, where the coordinatively unsaturated complex [Mo(PNP(Me)-iPr)(CO)X2] is formed. DFT mechanistic studies reveal that the seven-coordinate complexes should be the thermodynamic as well as the kinetic products. Since [Mo(PNP(Me)-iPr)(CO)X2] is the observed product it suggests that the reaction follows an alternative path. Structures of representative complexes were determined by X-ray single crystal analyses.

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منابع مشابه

Carbon dioxide hydrogenation catalysed by well-defined Mn(i) PNP pincer hydride complexes† †Electronic supplementary information (ESI) available: Experimental procedures, NMR and IR spectra, atomic coordinates for DFT optimized structures and computational details, and crystallographic data for 2. CCDC 1520528. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc00209b Click here for additional data file. Click here for additional data file.

Consiglio Nazionale delle Ricerche (CN Organometallici (ICCOM), Via Madonna Firenze, Italy. E-mail: [email protected] Institute of Applied Synthetic Chemist Getreidemarkt 9/163-AC, A-1060 Wien, Aust Institute of Chemical Technologies and An Getreidemarkt 9/163-AC, A-1060 Wien, Aust Centro de Qúımica Estrutural, Instituto Sup Rovisco Pais No. 1, 1049-001 Lisbon, Portug † Electronic supplement...

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عنوان ژورنال:

دوره 45  شماره 

صفحات  -

تاریخ انتشار 2016