Transition-metal complexes containing phosphorus ligands. Part II. Triaryl phosphite derivatives of ruthenium and osmium

Abstract

Simple metathetical replacement reactions have been utilised to synthesise some triaryl phosphite complexes MX,[P(OR),], ( M = Ru or 0 s ; X = CI, Br, or I ) from the corresponding triphenylphosphine derivatives MX2(PPh,), ( x = 3 or 4). Carbonyl and nitrosyl derivatives MX,(CO) [P(OR),],, MX,(CO),[P(OR),],, and MX,(NO)[P(OR),],have also been prepared. The complexes RuHX(PPh,), (X = CI or Br) have been shown to undergo metathetical exchange to form triaryl phosphite complexes which react further, with elimination of a molecule of hydrogen, to yield organo-ruthenium (11) species. Structures containing a o-bond between the central ruthenium atom and an ortho-carbon atom of one of the aryl rings are proposed for these latter derivatives and supporting spectroscopic evidence is discussed.

Competing Pathways in the Photochemistry of Ru(H)2(CO)(PPh3)3

“…Complex 1 (Scheme 1) has been characterized previously, 15,34 but a summary of its main spectroscopic features is provided in Scheme 1 and a 1 H NMR spectrum of the key hydride region is illustrated in Figure 1a; a 31 P{ 1 H} NMR spectrum is shown in the Supporting Information.…”

Ruthenium(II)Phosphite Complexes as Catalysts for the Hydrogenation of Carbon Dioxide

“…[15] One singlet in the 31 P NMR spectra of these compounds (1 a-c: d = 126-127; 1 d: d = 110.9 ppm) confirmed the trans orientation of the two chlorido ligands in the octahedral coordination sphere of the complexes. [15] One singlet in the 31 P NMR spectra of these compounds (1 a-c: d = 126-127; 1 d: d = 110.9 ppm) confirmed the trans orientation of the two chlorido ligands in the octahedral coordination sphere of the complexes.…”

The mechanistic investigations of photochemical decarbonylations and oxidative addition reactions for M(CO)5 (M = Fe, Ru, Os) complexes

“…[33][34][35][36][37] Along the entire group 8 metal triad (Fe, Ru, and Os), the photochemistry of Ru(CO) 5 and Os(CO) 5 has not been the subject of extensive study. [38][39][40][41][42][43][44][45][46][47] The reason for this could be that iron is cheap and environmentally benign but ruthenium and osmium are expensive and toxic. The instability of the Ru(CO) 5 and Os(CO) 5 complexes with respect to the respective formation of the well-known Ru 3 (CO) 12 and Os 3 (CO) 12 species could be another reason.…”

“…[54][55][56][57][58][59][60][61] However, both Ru(CO) 4 and Os(CO) 4 are predicted to have a singlet ground state. [38][39][40][41][42][43][44][45][46][47] In particular, iron tetracarbonyl fragments are an exceedingly active catalyst, as mentioned previously, [11][12][13][14][26][27][28] but ruthenium and osmium tetracarbonyl fragments are not easily formed photochemically from the corresponding M(CO) 5 reactants, because unlike Fe(CO) 4 , these can be produced but immediately combine with one CO molecule. [11][12][13][14][38][39][40][41][42][43][44][45][46][47] The activation of the Si-H bond in alkylsilane by this a d 8 organometallic photoproduct Fe(CO) 4 has been studied using picosecond time-resolved infrared (TRIR) spectroscopy.…”

“…[38][39][40][41][42][43][44][45][46][47] In particular, iron tetracarbonyl fragments are an exceedingly active catalyst, as mentioned previously, [11][12][13][14][26][27][28] but ruthenium and osmium tetracarbonyl fragments are not easily formed photochemically from the corresponding M(CO) 5 reactants, because unlike Fe(CO) 4 , these can be produced but immediately combine with one CO molecule. [11][12][13][14][38][39][40][41][42][43][44][45][46][47] The activation of the Si-H bond in alkylsilane by this a d 8 organometallic photoproduct Fe(CO) 4 has been studied using picosecond time-resolved infrared (TRIR) spectroscopy. [62][63][64][65][66] Therefore, if the reactants and products have different spin states, the way in which the species in a particular spin state transform into the nal products of the same spin state by way of several intermediates of different spin state and the spin crossovers is of interest.…”