A tribute to Professor John R. Moss

Alkenyl complexes of platinum group metals: a platform for diverse reactivity patterns

“…Among these, the chelating diphosphines such as dppe, dppp and dppm impart better relatively stability to the metal carbon bonds. [79] Subtle changes in the ligands bound to a metal often provide the basis for important chemical transformations as well as modifications of catalytic processes. In this regard, the reactivity of both mono and bis(1-alkenyl)-metal complexes shows distinct pathways, including (a) reaction at the M-C bond, (b) reaction at the C¼C bond, (c) coordination of pendant alkene and (d) reaction at electron-deficient metal centers as shown in Fig.…”

“…Metal-alkyls, alkenyls and metallacycloalkanes are very well documented species among the classical organometallic compounds, and they play a vital role in many synthetic and catalytic reactions. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] Ever since the preparation of the first metal-alkenyl complex reported by Green and Smith, valuable insights into the mechanistic details of these reactions have been elucidated, including both thermodynamic and kinetic aspects. [17] The chemistry of metal-alkenyls has experienced a notable development during the last few years, in part due to their involvement in different catalytic processes and their applications in organic synthesis, some of which can be found in the currently available literature.…”

“…[17] The chemistry of metal-alkenyls has experienced a notable development during the last few years, in part due to their involvement in different catalytic processes and their applications in organic synthesis, some of which can be found in the currently available literature. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][18][19][20][21][22][23] M-alkenyl complexes have been postulated as key intermediates in the Fischer-Tropsch process [24] and ethylene oligomerization reactions [25] including the generation of thin platinum films [26] for micro-electronic and catalytic applications [27] through the chemical vapor deposition (CVD) method. [28] Various factors influencing reactivity and mechanism in the chemical vapor deposition of the late transition elements from organometallic precursors including metal-alkenyls were discussed extensively.…”

“…The chemical properties are rather different from other known metal complexes of substituted alkyl or aryl complexes. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] Since then, the chemistry of metal-alkenyls of platinum group metals (PGM) has been a current research topic in our laboratories, and a review on the exciting chemistry of metal-alkenyls would be worthwhile. The earlier review on metal-alkenyl complexes was mainly focused on synthetic methodologies but the current review emphasizes the reactivity aspects of the title compounds.…”

“…The earlier review on metal-alkenyl complexes was mainly focused on synthetic methodologies but the current review emphasizes the reactivity aspects of the title compounds. [3] In order to keep the matter within reasonable limits, even though various metal complexes with heteroatoms like S, N and O in the alkenyl chains have been reported, including [Ru[S 2 CN(CH 2 CH¼CH 2 ) 2 ](dppm) 2 ] + , [44] but the present review does not focus on the heteroatoms containing alkenyl chains. Metal-vinyl, metal-allyl and metal-carbenes were also not included in this review.…”