Frustrated Lewis pairs

Even more effective in hydrogen activation are frustrated Lewis pairs [220] containing NHCs as Lewis bases. In 2008 two research groups reported the activation of hydrogen by frustrated Lewis pairs made up from a suitably Af,A -substituted NHC and B(CgF5)3 (Fig. 30) [221, 222]. The corresponding reaction of the frustrated Lewis pair with primary and secondary alkyl amines resulted in the formation of aminoboranes [222]. 

CT-VPP-REDOR) or the pulse duration fp (CT-VPD-REDOR) then produces CT-REDOR curves, from which the second moment may be evaluated with distinctively superior accuracy as compared to the values obtained from a parabolic fit to the conventional REDOR data. When restricting the experiment to short dipolar evolution times, the two-spin approximation may be applied for the data analysis, which proves to be especially attractive for amorphous solids, for which the exact spin geometry is unknovm. The data presented on the model compoimds illustrate the various facets of CT-REDOR NMR spectroscopy. First application examples, namely, the evaluation of the heteronuclear Li-Ti dipolar couplings within the garnet structure of Li5La3Nb20i2, the determi-nation of the intemuclear B- P distance in frustrated Lewis pairs, the analysis of Na- F dipolar interaction in fluormica or Na- P... 

In the framework of Frustrated Lewis Pairs, Erker also investigated the hydroboration of a-alkenyl-phosphines with HB(C6F5)2.52/53 Starting from dimesityl(vinyl)phosphine, the CH2CH2-bridged PB 40a was first... 

For example, if the BN bond were to break during the dehydrohalogenation process amine bases could be chosen that selectively capture a proton while the halogenated boron species remains uncoordinated due to steric hindrance. This concept is related to the recently published frustrated Lewis pair concept used for hydrogen activation by sterically demanding borane and amine species [104]. 

Frustrated Lewis Pairs A Metal-Free Strategy for Hydrogenation Catalysis... 

I 77 Frustrated Lewis Pairs" A Metal-Free Strategffor Hydrogenation Catalysis... 

The unique reactivity of the above system with H2 appears to arise from the unquenched Lewis basicity and acidity of the respective donor P and the acceptor B centers. This inference prompted questions about the nature and reactivity of other phosphine-borane systems and, more broadly, of Lewis acid/base combinations. Is it necessary to have a link between the donor and acceptor sites Could similar H2 activation arise from combinations of donors and acceptors in which steric encumbrance frustrates Lewis acid-base adduct formation If indeed such frustrated Lewis pairs could be uncovered, could one exploit them for the activation of small molecules and applications in catalysis ... 

I 77 Frustrated Lewis Pairs A Metal-Free Strategy for Hydrogenation Catalysis Table 11.1 Catalytic hydrogenation of imines with phosphonium borate catalysts [45]. 

Does the presence of excessive steric bulk when a Lewis acid and a Lewis base attempt to form an adduct automatically render these species inert towards each other The unique behavior of sterically frustrated Lewis pairs (FLPs), pioneered by Stephan, is a vigorous research area with applications for small molecule activation and catalysis." The highly Lewis acidic and sterically bulky tris(pentafluorophenyl)borane" plays a role in many FLP reactions. The great promise of FLP chemistry was revealed by reactions between tris(pentafluorophenyl)borane and tertiary and secondary phosphines, where sterics preclude formation of classic adducts. A seminal example of a frustrated Lewis pair is that of the secondary phosphine di(2,4,6-trimethylphenyl)phosphine that is precluded from forming a classic adduct with tris(pentafluorophenyl)borane. The phosphine Lewis pair is frustrated since it cannot interact with boron to form the adduct. 

Spectacular small molecule activation has been achieved with FLPs, including with 1 2 and N20. The chanistry enabled by frustrated Lewis pairs is being exploited to develop non-transition-metal catalysts that promise to substitute for catalysts that contain toxic and expensive heavy metals. ... 

The ability of frustrated Lewis pairs to capture NO (nitric... 

Berke H, Jiang Y, Yang X, Jiang C, Chakraborty S, Landwehr A (2013) Coexistence of Lewis acid and base functions a generalized view of tbe frustrated lewis pair concept with novel implications for reactivity. Top Curr Cbem 334. doi 10.1007/128 2012 400... 

As an example, the results for formation of the donor-acceptor bond in MejN-BMCj are shown in Figure 16.4. Such bonds (and their strengthening by dispersion and weakening by EXR effects) play an important role in the so-called frustrated Lewis pairs (FLP), which have attracted enormous attention recently because of their ability to activate small molecules such as H2 [35-37]. Because the bond dissociates heterolyticaUy into closed-shell fragments, static electron correlation effects play no important role and a standard restricted DFT treatment... 

We recently initiated efforts within our own laboratory to synthesize terpy-based ligands that incorporate appended Lewis acid/base pairs [36]. Motivated by metal-free systems of frustrated Lewis pairs (FLPs) which bind and form adducts with small molecules, we sought to couple the reactivity of FLPs to a transition-metal fragment to afford a metal Lewis acid/base triad (LABT). The combination of both partners with a transition-metal center opens up the possibiUty to synergistically use these systems for further activation and/or redox transformations - currently a hmitation of metal-free FLP systems. 

Zwitterionic Polymerization by Classical and Frustrated Lewis Pairs... 

The seminal works [288-294] of Stephan and Erker uncovered the concept of Frustrated Lewis Pairs (FLPs) to describe sterically encumbered borane Lewis acid (most commonly B(C6p5)3) and base (e.g., BU3P) pairs that are sterically... 

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