Main-group and transition-metal complexes of bis(phosphinimino)methanides

Abstract

Bis(phosphinimino)methanides exhibit a wide variety of coordination chemistry with almost all elements in the periodic table. This critical review deals with the chemistry and coordination behavior of bulky monoanionic {CH(PPh(2)NR)(2)}(-) bis(phosphinimino)methanide and dianionic {C(PPh(2)NR)(2)}(2-) bis(phosphinimino)methanediide (R = SiMe(3), aryl) ligands focusing on s- and p-block as well as transition metals (109 references).

Bis(phosphinimino)methanide Borohydride Complexes of the Rare‐Earth Elements as Initiators for the Ring‐Opening Polymerization of ε‐Caprolactone: Combined Experimental and Computational Investigations

“…The ring adopts a typical twist-boat conformation in which the central carbon atom and the lanthanum atom are displaced from the N 2 P 2 least-squares plane. [66] As expected, a weak interaction between the central carbon atom (C1) and the lanthanum atom is observed (LaÀC1 2.789 (3) ). This distance is longer than observed for normal LaÀC bonds.…”

“…[39] The general polymerization process, especially the key step of the formation of the propagating species as an aliphatic alkoxide with a terminal CH 2 OBH 2 group, proceeds by a well-demonstrated, both experimentally and theoretically, and a well-accepted mechanism that is common to all borohydride initiating species. [39,[43][44][45][46][47][48] Recently, we introduced the bis(phosphinimino)methanide {CH(PPh 2 NSiMe 3 ) 2 } À , which has been used previously by a number of research groups in main-group and transition-metal chemistry, [63][64][65][66] into yttrium and lanthanide chemistry as a replacement for cyclopentadienyl. [51,[67][68][69][70][71][72][73][74][75] In general the CH 2 (PPh 2 NSiMe 3 ) 2 ligand is very easily accessible.…”

Coordination Behavior of the S–C–S Monoanion and O–C–O and S–C–S Dianions toward CoII

“…- [1] and 1 2-, [2] respectively, and of the dianion of bis(thiophosphinoyl)methane, 2 2-, [3] has been studied in depth (Scheme 1), especially in the past decade. [4] In particular, dianions 1 2-and 2 2- March 17, 2010 Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/ejic.201100144.…”

Methanediide Formation via Hydrogen Elimination in Magnesium versus Aluminium Hydride Complexes of a Sterically Demanding Bis(iminophosphoranyl)methanediide

“…Complexes of methanediides (methandiides) that derive from P-oxidized bis(diphenylphosphino)methane species with electropositive metals have especially attracted widespread interest in recent years [2][3][4][5][6][7][8]. In these complexes, the dianionic bis(diphenylphosphoranyl)methanediide fragment A shows overall delocalization of the charge across the EPCPE fragment with a simplified charge distribution as shown in Figure 1.…”

“…This delocalization allows the deprotonation of both hydrogen atoms of the central CH 2 unit of the substituted "methane" pro-ligand with suitable strong bases. Methanediides show several bonding modes containing typically one or two coordinated metal centres [2][3][4][5][6][7][8]. Over the past years, several examples of alkaline earth metal complexes of substituted bis(phosphoranyl)methanides and -methanediides have been forthcoming [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23] that show several coordination types B-E, see Figure 1.…”