Cyclic (Amino)(Phosphonium Bora‐Ylide)Silanone: A Remarkable Room‐Temperature‐Persistent Silanone

Abstract

As ilanone substituted by bulkya mino and phosphonium bora-ylide substituents has been isolated in crystalline form. Thanks to the exceptionally strong electron-donating phosphonium bora-ylide substituent, the lifetime at room temperature of the silanone is dramatically extended (t 1/2 = 4days) compared to the related (amino)(phosphoniumylide)silanone VI (t 1/2 = 5h), allowing easier manipulation and its use as precursor of new valuable silicon compounds.T he interaction of silanone with aweak Lewis acid such as MgBr 2 increases further its stability (no degradation after 3weeks at room temperature).Incontrast to carbonyl compounds (I), probably one of the most important functional group in organic chemistry,t he heavier silicon analogue,s ilanones (II), are generally highly reactive transient species [1] that were only observed either in argon matrix at low temperature [2] or in the gas phase [3] and were evidenced by trapping reactions. [4] Silanones present as trongly polarized Si=Od ouble bond (Si d+ ÀO dÀ )w ith ac onsiderably large bond energy difference between SiO-p and SiO-s bonds, [5] and therefore,t hey easily oligomerize to give polysiloxanes. [6] Recently,e asy-to-handle silanones stabilized as donor-acceptor or donor complexes,h ave been reported. [7][8][9][10][11] Nevertheless,t he synthesis of stable threecoordinate silanone derivatives remains ad ifficult task, although the heavier analogue germanone III,well kinetically stabilized by bulky aryl substituents,h as been isolated by Matsuo/Tamao et al. [12] At present only three examples are reported:1 )the transition-metal-substituted silanone IV, isolated at RT by Filippou et al., [13] 2) the cyclic dialkylsilanone V,c haracterized in situ at À80 8 8Cb yt he group of Iwamoto, [14] and 3) the relatively persistent (amino)-(ylide)silanones VI,r eported by us. [15] Therefore,t heir synthetic use is still limited because of the scarcity and limited lifetime (0.5-5 h, at RT for VI). Herein we report that the introduction of as trongly donating phosphonium boraylide substituent considerably extends the lifetime of silanone 2 (t 1/2 = 4days,a tR T), which allows easier manipulation to study its properties and reactivity.Recently,w eh ave described that the electropositive boron-based substituent (phosphonium bora-ylide), [16,17] with an exceptionally strong electron donating character,i s able to efficiently stabilize highly reactive species such as Nheterocyclic silylene 1,the related silylium ion and transitionmetal-silylene complexes featuring at rigonal-planar geometry around the silicon center. [18] We thus have considered the use of the same set of substituents for the stabilization of the silanone moiety.T aking into account the better donating ability of phosphonium bora-ylide function than that of classical (carbo)ylides, [18] we can expect abetter stabilization effect with this substituent set than that used for the previously persistent silanone VI.The( amino)(bora-ylide)silylene 1 [15] immediately reacts with N 2 Oi nT HF solution, at À20...

Bonding Relationship between Silicon and Germanium with Group 13 and Heavier Elements of Groups 14–16

“…In 2017, Kato et al . isolated a cyclic(amino)(phosphonium‐bora‐ylide)silanone, stabilized by two different π‐donating substituents, an amino group and a more electropositive boron‐based π‐donating phosphonium boraylide functional group [85b] . Later in 2019, Iwamoto and co‐workers synthesized and isolated kinetically stabilized silicon analogue of a ketone with the unperturbed Si=O moiety, which represents the first example of isolable genuine silanone compound [85c] .…”

An Isolable Bis(Silanone–Borane) Adduct

“…[21] Addition of B(C 6 F 5 ) 3 to ac yclic amino(bora-ylide(silanone)) reported by Kato et al,i ncreased the stability of the pre-formedf ree silanone. [22] In the presence of B(C 6 F 5 ) 3 ,R oesky et al accomplished the isolation of ad onor-acceptor stabilized silaformyl chloride. [14] However,i solation of ab orane-stabilized silanone startingf rom as ilylene-borane system is not reported so far.…”

Synthesis of a Stable N‐Hetero‐RhI‐Metallacyclic Silanone

“…Zuschriften efficiently stabilize a trigonal planar geometry of Si atom. [12,13,22] These probably explain the adaptation of square planar geometry of Rh I atom (weak p-donation and strong s-donation) rather than tetrahedral one (strong pdonation and strong s-acceptation). It should be noted that the silanone 2 with a tetrahedral Rh I group is not a minimum on the energy surface.…”

“…[18] The molecular structure of silanone 2 [19] reveals a planar geometry around the three-coordinated silicon atom (S si 8 = 358.398) and a short Si=O bond length [1.540 (3) ] which is longer than those of chromium-substituted silanone I (1.526 ) [10] and of dialkylsilanone V (1.518 ) [14] but is similar to those observed for other p-donor substituted silanones II-IV (1.533-1.543 ). [11][12][13] The N1-Si1 bond length [1.775 3] is almost identical to that of silylene 1 (1.771-1.781 ). Although the Si1-Rh bond [2.237(1) ] is slightly elongated compared to those of 1 (2.141-2.174 ), it is still shorter than classical Si(sp 2 )-Rh I bonds (2.30-2.35 ), [20] which suggests a remaining Rh-Si p-interaction.…”

“…However, the synthesis of stable "base-free" silanones remains a difficult task. Indeed, although the recent studies demonstrated that bulky or/and strongly s-or/and p-donating substituents efficiently stabilize silanones I-V enough to be isolated in the crystalline form, [10][11][12][13][14] most of them remain unstable in solution at room temperature. To the best of our knowledge, only two silanones, such as the chromium-substituted cationic silanone I [10] and cyclic dialkylsilanone V, [14] are stable in solution at RT.…”