Rutheniumkomplexe mit Diazadienen, VI [1] η⁶-Cycloheptatrien-und η⁴ -Norbornadien-diazadien-ruthenium(0)-Komplexe / Ruthenium Complexes with Diazadienes, VI [1] η⁶-Cycloheptatriene-and η⁴-Norbornadiene-diazadiene-ruthenium(0) Complexes

Abstract

<jats:title>Abstract</jats:title><jats:p> Reduction of [(cyclo-C<jats:sub>7</jats:sub>H<jats:sub>8</jats:sub>)RuCl<jats:sub>2</jats:sub>]<jats:sub>2</jats:sub> in the presence of a diazadiene RN=CH−CH=NR (DAD; R = i-C<jats:sub>3</jats:sub>H<jats:sub>7</jats:sub>) gives red, airsensitive, sublimable (η<jats:sup>6</jats:sup>-C<jats:sub>7</jats:sub>H<jats:sub>8</jats:sub>)Ru(DAD) (5). A rigid structure on the basis of the <jats:sup>1</jats:sup>H NMR spectrum is excluded. On the other hand pentacoordinate complexes [η<jats:sup>4</jats:sup>-nor-C<jats:sub>7</jats:sub>H<jats:sub>8</jats:sub>)Ru(DAD)P(C<jats:sub>6</jats:sub>H<jats:sub>5</jats:sub>)<jats:sub>3</jats:sub>] (8) or [(η<jats:sup>4</jats:sup>-nor-C<jats:sub>7</jats:sub>H<jats:sub>8</jats:sub>)Ru(DAD)CO] (9) have rigid, C<jats:sub>s</jats:sub>-symmetric, square-pyramidal structures. They are obtained by chemical or irreversible electro-chemical reduction of [(η<jats:sup>4</jats:sup>-nor-C<jats:sub>7</jats:sub>H<jats:sub>8</jats:sub>)Ru(DAD)Cl<jats:sub>2</jats:sub>] to [η<jats:sup>4</jats:sup>-nor-C<jats:sub>7</jats:sub>H<jats:sub>8</jats:sub>)Ru(DAD)(solv)] (7) (solv = tetrahydrofuran or acetonitrile) and addition of phosphine or carbon monoxide. 7, in non-coor-dinating solvents, is a stereospecific catalyst for the 1-alkene → trans-2,... -alkene isomerization.</jats:p>

Complexes of Ruthenium and Osmium Containing η2–η6 Hydrocarbon Ligands: (iii) Complexes Containing Six-, Seven- and Eight-membered Rings

“…295 Reduction of a mixture of [ {RuCl 2 (r| 6 -chpt)} 2 ] and the diazadiene Pr i N=CHCH=NPr i (dad) with lithium sand gives the red, zero-valent metal complex [Ru(r| 6 -chpt)(dad)]. 296 Treatment of [{RuCl 2 ('n 6 -chpt)} 2 ] with piperidine gives a highly air-sensitive, yellow piperidide [RuCl(C 5 H 10 N)(C 5 H 10 NH) 2 (T| 4 -chpt)] containing bidentate chpt; the piperidine ligands are displaced by treatment with various bulky diazadienes to give blue or violet complexes of Ru IV (62) whose NMR spectra indicate that chpt adopts an unusual l-5:7r|-bonding mode. 297 Cycloocta-l,3,5-triene is readily displaced from [Ru(l-3:5,6r|-C 8 H u )(T|-l,3,5-C 8 H 10 )]PF 6 by CO and Bu'NC to give [Ru(L) 3 (l-3:5,6ri-C 8 H 11 )]PF 6 , and by group 1 5 donors to give [Ru(L) 3 (l-5T]-C 8 H n )]PF 6 (L = P(OMe) 3 , PMe 2 Ph*, AsMe 2 Ph, A s M e P h 2 ) ; 2 * 5 ' 2 ® 6 the change in bonding mode is probably determined largely by the steric bulk of the group 1 5 donors, as l-5r|-C 8 H n has a smaller cone angle than l-3:5,6n-C 8 H,,.…”

Complexes of Ruthenium and Osmium Containing η2–η6 Hydrocarbon Ligands: (i) Complexes not Containing Cyclobutadiene, Cyclopentadienyl or η-Arene Coligands

“…Similarly, [Ru(CO) Anionic hydrido(l,3-diene)ruthenium(0) complexes containing tertiary phosphines as coligands are obtained by reaction o f dienes with anionic hydrides (Equations(9)and(10)). The neutral complex [RuH 4 (PPh 3 ) 3 ] reacts with butadiene to give [Ru(PPh 3 ) 3 (r|-C 4 H 6 )], whereas with 1,4-diphenylbutadiene the product is a dihydridoruthenium(II) complex, Reduction of [RuCl 2 (dad)(r|-nbd)] (dad = Pr i N=CHCH=NPr i ) with lithium in the presence of PPh 3 or CO affords red, zerovalent metal complexes [Ru(L)(dad)(r|-nbd)], which are probably square pyramidal 127. …”