1,1-Diboration of Isocyanides with [2]Borametalloarenophanes

Abstract

A series of new [3]diboracarbametalloarenophanes was synthesized by reaction of [2]borametalloarenophanes or [3]diboraplatinametalloarenophanes with isocyanides and was fully characterized by multinuclear NMR spectroscopy and, in the case of [Fe{η 5 -C 5 H 4 B(NMe 2 )} 2 CdN-t-Bu], additionally by X-ray diffraction analysis.

Synthesis of a distanna [2]ferrocenophane and reactivity of [2]ferrocenophanes towards elemental sulfur and selenium

“…The reaction mixture was stirred for 4 h. All volatile components were removed in vacuo, the orange precipitate was extracted into pentane and all insoluble material ppm. 13 [Fe(h 5 -C 5 H 4 BNMe 2 ) 2 S] (10): 245 mg (0.86 mmol) of 5 dissolved in 10 mL toluene were treated with an excess of sulfur (100 mg, 3.12 mmol). After 24 h, the red solution brightened and all volatile compounds were removed in vacuo.…”

“…The catalytically active species, a 1,3-dibora-2-platina [3]ferrocenophane, was isolated and structurally characterized [12]. This reactivity pattern was successfully transferred to other systems and for the first time, the diboration of the NeN double bond in azobenzene and the 1,1 0 -diboration of isocyanides was demonstrated [13,14]. It should be noted, that for the reaction of 4 with alkynes, an alternative heterogeneous catalyzed synthetic protocol was developed as well [12] (Scheme 2).…”

Unexpected Generation of Diastereomers by Double Diboration of a Dialkyne

“…[29] By expansion of this strategy, we also achieved the diboration of diazo compounds [16] and isocyanides. [30] Herein, we report on the two diastereomeric [4]diboradicarbaferrocenophanes 4 and 5, which were obtained by double diboration of the conjugated dialkyne 3 either by a platinum-mediated route employing the [2]boraferrocenophane 1 in the presence of [PtA C H T U N G T R E N N U N G (PEt 3 ) 3 ], or stoichiometrically by using the [3]diboraplatinaferrocenophane 2, directly (Scheme 1). In contrast to related transformations of monoalkynes, [29] monitoring the reaction progress by multinuclear NMR spectroscopy revealed the gradual disappearance of the starting materials, and the formation of two distinct compounds in benzene solution at elevated temperatures.…”

Ansa‐Complexes of [Mn(η5‐C5H5)(η6‐C6H6)]: Preparation, Characterization, and Reactivity of [n]Manganoarenophanes (n=1, 2, 3)

“…[18] Reactivity studies on these metalloarenophanes revealed their potential for further transformations, such as ringopeningp olymerization [7,[10][11][12] to produce metallopolymers or the functionalization of unsaturated organic substrates. [19][20][21][22][23][24][25][26][27][28] Herein, we focus on the manganese-containing complex [Mn(h 5 -C 5 H 5 )(h 6 -C 6 H 6 )],w hichi si soelectronic to ferrocene. Alongside [Cr(h 5 -C 5 H 5 )(h 6 -C 6 H 6 )] it represents ar are example of as ystem with ab enzene and ac yclopentadienyl ligand that has successfullyb een employed for the preparation of ansacomplexes.…”