Syntheses and structures of dimeric sodium and potassium complexes of 2,6-diisopropyl-anilidophosphine borane ligand

Abstract

We report here the syntheses and structural studies of dimeric sodium and potassium complexes of composition [Na(THF) 2 {Ph 2 P(BH 3)N(2,6-i Pr 2 C 6 H 6)}] 2 (2) and [K(THF) 2 {Ph 2 P(BH 3)N(2,6-i Pr 2 C 6 H 6)}] 2 (3). The sodium complex 2 was readily prepared by the reaction of sodium bis(trimethylsilyl)amide with 2,6diisopropylanilidophosphine-borane ligand [2,6-i Pr 2 C 6 H 3 NHP(BH 3)Ph 2 ](1-H) at ambient temperature. The potassium complex 3 was prepared by two synthetic routes: in the first method, the ligand 1-H was made to react with potassium hydride at room temperature to afford the corresponding potassium complex. The potassium bis(trimethylsilyl)amides were made to react with protic ligand 1-H in the second method to eliminate the volatile bis(trimethyl)silyl amine. Solid-state structures of both the new complexes were established by single crystal X-ray diffraction analysis. In the molecular structures of complexes 2, the sodium metal is coordinated by the anilido nitrogen (η 1) and borane group (η 1) attached to the phosphorus atom of ligand 1. In contrast, for compound 2, ligand 1 displays η 6 π-arene interaction from 2,6-diisopopylphenyl ring with potassium atom along with η 3 interaction of BH 3 group due to larger ionic radius of potassium ion.

New sandwich-type polymeric potassium-dicyanoargentate(I) complex: synthesis, characterization and enzymatic activity

“…In addition to the CN ligand in the structure, it formed a heteroleptic dicyanidoargentate complex Potassium atoms are connected together in the form of cubes intertwined by the binding of N atoms above and below the plane ( Figure 5). Here, the K atoms exhibited a structure similar to the 6 coordinated K complexes in the literature [38][39][40]. interesting contributions to the stacking of the complex ( Figure 6).…”

Mononuclear Aluminum Complexes as Precursors for Cyanosilylation of Carbonyl Compounds

“…[5][6][7][8] Our group has been working to understand the coordination behavior of a series of chelating phosphine amines [Ph 2 PNHR] (R = 2,6-Me 2 C 6 H 3 , CHPh 2 , CPh 3 ) and their chalcogen derivatives [Ph 2 P-(O)NHR] (NPO), [Ph 2 P(S)NHR] (NPS) and [Ph 2 P(Se)NHR] (NPSe) with alkali metals, alkaline-earth metals, and main-group metals. [9][10][11][12] We observed that in many cases the chalcogen moiety of these ligands also efficiently coordinated to a metal center along with nitrogen centers and subsequently stabilized highly oxophilic metal complexes and enhanced their catalytic reactivity. These complexes have shown excellent catalytic activity during various organic transformations.…”

“…Of such hybrid ligands, a variety of amido phosphine chelating ligands, including bidentate amido phosphine [NP] − , tridentate amido diphosphine [PNP] − , and tridentate diamido phosphine [NPN] 2− , have shown extensive reactivity with several metals in the periodic table [5–8] . Our group has been working to understand the coordination behavior of a series of chelating phosphine amines [Ph 2 PNHR] (R=2,6–Me 2 C 6 H 3 , CHPh 2 , CPh 3 ) and their chalcogen derivatives [Ph 2 P(O)NHR] (NPO), [Ph 2 P(S)NHR] (NPS) and [Ph 2 P(Se)NHR] (NPSe) with alkali metals, alkaline‐earth metals, and main‐group metals [9–12] . We observed that in many cases the chalcogen moiety of these ligands also efficiently coordinated to a metal center along with nitrogen centers and subsequently stabilized highly oxophilic metal complexes and enhanced their catalytic reactivity.…”

Polymerization of ϵ‐Caprolactam to Nylon‐6 Catalyzed by Barium σ‐Borane Complex under Mild Condition

“…[21][22][23][24][25][26][27][28][29] In addition to intense energy requirements, these high-temperature reactions have several other drawbacks, including the formation of undesired side products. [42][43] Although the catalytic efficacy of alkali/alkaline metal and their respective hydrides in the ring-opening polymerization of caprolactam in harsh condition has been well documented, reports involving the catalysis of σ-borane complex of Ae metal are scarce. These side reactions are strongly marked by weak heat exchange with the surrounding medium during typical bulk polymerization.…”

“…[32][33][34][35][36][37][38][39][40] In a related context, a dual site catalyst system has been developed using a boratependant ruthenium complex in which the ruthenium center plays the role of an activating group and the boron center acts as the hydride donor to render selective reduction of the C�N bond. [42][43] Although the catalytic efficacy of alkali/alkaline metal and their respective hydrides in the ring-opening polymerization of caprolactam in harsh condition has been well documented, reports involving the catalysis of σ-borane complex of Ae metal are scarce. [42][43] Although the catalytic efficacy of alkali/alkaline metal and their respective hydrides in the ring-opening polymerization of caprolactam in harsh condition has been well documented, reports involving the catalysis of σ-borane complex of Ae metal are scarce.…”