Borate Esters as Alternative Acid Promoters in the Palladium‐Catalyzed Methoxycarbonylation of Ethylene

Abstract

Unkonventionell! Die Verwendung von Borosalicylsäure, die sich aus Bor‐ und Salicylsäure ableitet, als saurer Beschleuniger der Methoxycarbonylierung von Ethen zu Methylpropionat wurde untersucht (siehe Schema). Dabei wurde nicht nur eine akzeptable Katalysatoraktivität festgestellt, sondern auch eine viel geringere Bildung von Phosphoniumsalzen als mit konventionellen Säuren.

Bis[N,N-bis(diphenylphosphanyl)cyclopentanamine-κ2P,P′]platinum(II) bis(trifluoromethanesulfonate)

“…Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999 Farrar et al, 1995;Dyson et al, 2004;Cloete et al, 2010;Engelbrecht et al, 2010a,b. Diphosphinoamine (PNP) and other P donor ligands (Keat et al, 1981;Purcell et al, 1995;Cotton et al, 1996;Otto & Roodt, 2001;Fei et al, 2003;Otto et al, 2005;Muller et al, 2008;Engelbrecht et al, 2010c,d;2011) with various substituents on both the P and N atoms form part of ongoing research in different catalytic olefin transformation reactions such as hydroformylation (Haumann et al, 2004;Crous et al, 2005), metathesis (Booyens et al, 2007) and methoxycarbonylation (Ferreira et al, 2007).…”

“…For diphosphinoamine (PNP) and other P-donor ligands, see: Keat et al (1981); Purcell et al (1995); Cotton et al (1996); Otto & Roodt (2001); Fei et al (2003); Otto et al (2005); Muller et al (2008); Engelbrecht et al (2010cEngelbrecht et al ( ,d, 2011. For their use in catalytic olefin transformation reactions, see: Haumann et al (2004); Crous et al (2005); Booyens et al (2007); Ferreira et al (2007). For puckering parameters, see: Cremer & Pople (1975).…”

N,N-Bis(diphenylphosphanyl)cyclobutanamine

“…Diphosphinoamine (PNP) and other P donor ligands (Muller et al, 2008;Purcell et al, 1995;Otto et al, 2005;Otto & Roodt, 2001) with various substituents on both the P and N atoms form part of ongoing research in different catalytic olefin transformation reactions such as hydroformylation (Haumann et al, 2004;Crous et al, 2005), metathesis (Booyens et al) methoxycarbonylation (Ferreira et al, 2007) and tetramerization (Cloete et al, 2011). In the title compound, C 29 H 29 NP 2 , Fig.1, all bond distances and angles fall within the range for similar complexes (Keat et al, 1981;Cotton et al, 1996;Fei et al, 2003;Cloete et al, 2008Cloete et al, , 2009Cloete et al, , 2010Engelbrecht et al, 2010aEngelbrecht et al, , 2010b.…”

“…For diphosphinoamine (PNP) and other P-donor ligands, see: Muller et al (2008); Purcell et al (1995); Otto & Roodt (2001); Otto et al (2005). For their use in catalytic olefin transformation reactions, see: Haumann et al (2004); Crous et al (2005); Booyens et al (2007); Cloete et al (2011); Ferreira et al (2007).…”

Crystal structure of dichlorido(N-o-tolyl-1,1-di-p-tolylphosphanamine–κ1 P)-(methoxydi-p-tolylphosphane-κ1 P)palladium(II), C36H39Cl2NOP2Pd

“…The title complex forms part of an ongoing research study on the development of highly effective palladium, and platinum group metals in general, catalysts for various organic transformations [12][13][14][15][16][17][18][19]. The two Cl ligands on the title complex adopt a cis-conformation while the distorted square planar geometry is illustrated by a 93.83(2)°bond angle formed by the P-Pd-P bonds.…”