000098582 001__ 98582
000098582 005__ 20190527111140.0
000098582 0247_ $$2doi$$a10.1021/om060752n
000098582 02470 $$2ISI$$a000243577000020
000098582 02470 $$a9930$$2DAR
000098582 037__ $$aARTICLE
000098582 245__ $$aMechanistic Studies on the Formation of eta(2)-Diphosphine (eta(6)-p-cymene)ruthenium(II) Compounds
000098582 269__ $$a2007
000098582 260__ $$c2007
000098582 336__ $$aJournal Articles
000098582 520__ $$aA new range of pendent diphosphine (<i>η</i><SUP>6</SUP>-<I>p</I>-cymene)ruthenium(II) complexes, [RuCl(PPh<SUB>3</SUB>)(<i>η</i><SUP>1</SUP>-(P-P))(<i>η</i><SUP>6</SUP>-<I>p</I>-cymene)]PF<SUB>6</SUB> (P-P = dppm, <I>cis</I>-PPh<SUB>2</SUB>CHCHPPh<SUB>2</SUB> (dppv), dppe, dppp, dppf), have been prepared by substitution of the labile acetonitrile ligand in [RuCl(CH<SUB>3</SUB>CN)(PPh<SUB>3</SUB>)(<i>η</i><SUP>6</SUP>-<I>p</I>-cymene)]PF<SUB>6</SUB>. The formation of chelate complexes, [RuCl(<i>η</i><SUP>2</SUP>-(P-P))(<i>η</i><SUP>6</SUP>-<I>p</I>-cymene)]<SUP>+</SUP>, from these pendent phosphine complexes and from the related neutral complexes, [RuCl<SUB>2</SUB>(<i>η</i><SUP>1</SUP>-(P-P))(<i>η</i><SUP>6</SUP>-<I>p</I>-cymene)] (P-P = dppm, dppv), has been investigated, including determination of activation enthalpies (Δ<I>H</I><SUP>‡</SUP>) and entropies (Δ<I>S</I><SUP>‡</SUP>). A concerted substitution mechanism is proposed for the latter complexes, in which methanol plays an important role in the ring-closing process by formation of hydrogen bonds with the chloride ligands. This proposal is supported by volumes of activation (Δ<I>V</I><SUP>‡</SUP>) determined by variable-pressure UV-visible spectroscopy. In contrast, a dissociative mechanism is proposed for the series of cationic pendent phosphine complexes, which generally require higher temperatures to effect ring closure. Secondary reaction pathways can be observed in some cases and are discussed in terms of differences between the phosphine complexes and supplemented by investigations using electrospray ionization mass spectrometry (ESI-MS). The X-ray structures of [RuCl(PPh<SUB>3</SUB>)(<i>η</i><SUP>1</SUP>-(P-P))(<i>η</i><SUP>6</SUP>-<I>p</I>-cymene)]PF<SUB>6</SUB> (P-P = dppm, dppv, dppp) and [RuCl(<i>η</i><SUP>2</SUP>-dppv)(<i>η</i><SUP>6</SUP>-<I>p</I>-cymene)]PF<SUB>6</SUB> are also reported.
000098582 700__ $$0240381$$g161826$$aChaplin, AB
000098582 700__ $$0240336$$g148925$$aFellay, C
000098582 700__ $$g123171$$aLaurenczy, G$$0240013
000098582 700__ $$aDyson, PJ$$g149418$$0240015
000098582 773__ $$j26$$tOrganometallics$$k3$$q586-593
000098582 909C0 $$xU9$$0252010$$pLCOM
000098582 909CO $$pSB$$particle$$ooai:infoscience.tind.io:98582
000098582 937__ $$aLCOM-ARTICLE-2007-003
000098582 973__ $$rREVIEWED$$sPUBLISHED$$aEPFL
000098582 980__ $$aARTICLE