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Reactions of (mesityl)n(methyl)2−nsilylene complexes with pyridine-N-oxide (n = 1 and 0): formation of silanone complexes and a disiloxanyloxy complex
Dalton Transactions ( IF 4 ) Pub Date : 2024-04-03 , DOI: 10.1039/d4dt00631c Takako Muraoka 1, 2 , Taichi Ishita 1 , Kosuke Kawachi 1 , Takuya Nishio 1 , Hiroto Ishihara 1 , Keiji Ueno 1
Dalton Transactions ( IF 4 ) Pub Date : 2024-04-03 , DOI: 10.1039/d4dt00631c Takako Muraoka 1, 2 , Taichi Ishita 1 , Kosuke Kawachi 1 , Takuya Nishio 1 , Hiroto Ishihara 1 , Keiji Ueno 1
Affiliation
Silanones (O![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
SiR2), a heavier congener of ketones (R2CO), are highly reactive species that are readily converted to oligomeric siloxane (O–SiR2)n. Coordination of silanones to the transition-metal fragments to afford silanone-coordinated complexes is a reliable silanone stabilization method. Recently, our group reported the synthesis, structures, and reactivity of dimesityl-substituted silanone complexes Cp*(OC)2M{OSiMes2(L)}(SiMe3) (M = W, Mo, L: Lewis base, Cp*: η5-C5Me5, Mes: 2,4,6-Me3C6H2). Herein, to investigate the effect of substituents on the silicon atom during the formation of a silanone complex, we demonstrated the use of Mes and smaller Me groups. As a result, the formation of Mes(Me)-substituted silanone molybdenum complex Cp*(OC)2Mo{OSiMes(Me)(py)}(SiMe3) (5b, py: pyridine) was suggested, the silanone tungsten complex Cp*(OC)2W{OSiMes(Me)(DMAP)}(SiMe3) (4a, DMAP: 4-(dimethylamino)pyridine) was obtained, and a dimethyl-substituted disiloxanyloxy(dioxo) complex Cp*(O)2W(OSiMe2OSiMe3) (9) was formed. The reaction of 4a with PMe3 proceeded via the elimination of DMAP and migration of the SiMe3 group to the oxygen atom of the silanone ligand to afford Cp*(OC)2W(SiMes(Me)OSiMe3)(PMe3) (11a). The Mo complex Cp*(OC)2Mo(SiMes(Me)OSiMe3)(PMe3) (11b) was produced by the reaction of Cp*(OC)2Mo{SiMes(Me)}(SiMe3) (7b) with pyridine-N-oxide in the presence of PMe3.
中文翻译：
(异三叉基)n(甲基)2−n亚甲硅烷基络合物与吡啶-N-氧化物（n = 1 和 0）的反应：形成硅烷酮络合物和二硅氧烷氧基络合物
硅烷酮 (OSiR 2 ) 是酮 (R 2 CO )的较重同系物，是高反应性物质，很容易转化为低聚硅氧烷 (O–SiR 2 ) n。硅烷酮与过渡金属片段配位以提供硅烷酮配位络合物是一种可靠的硅烷酮稳定方法。最近，我们课题组报道了二三甲苯基取代硅酮配合物Cp*(OC) 2 M{O SiMes 2 (L)}(SiMe 3 ) (M = W, Mo, L: Lewis碱，Cp )的合成、结构及反应活性*：η 5 -C 5 Me 5、Mes：2,4,6-Me 3 C 6 H 2 )。在此，为了研究硅酮络合物形成过程中取代基对硅原子的影响，我们演示了 Mes 和更小的 Me 基团的使用。结果表明，形成了Mes(Me)取代的硅烷酮钼络合物Cp*(OC) 2 Mo{O SiMes(Me)(py)}(SiMe 3 ) ( 5b，py:吡啶)，即硅烷酮钨得到络合物Cp*(OC) 2 W{O SiMes(Me)(DMAP)}(SiMe 3 )( 4a，DMAP：4-(二甲基氨基)吡啶)，得到二甲基取代的二硅氧烷氧基(二氧代)络合物Cp*(形成O) 2 W(OSiMe 2 OSiMe 3 ) ( 9 )。 4a与 PMe 3的反应通过DMAP 的消除和 SiMe 3基团迁移至硅烷酮配体的氧原子进行，得到 Cp*(OC) 2 W(SiMes(Me)OSiMe 3 )(PMe 3 ) ( 11a）。 Mo络合物Cp*(OC) 2 Mo(SiMes(Me)OSiMe 3 )(PMe 3 ) ( 11b )是通过Cp*(OC) 2 Mo{ SiMes(Me)}(SiMe 3 ) ( 7b )反应生成的)与吡啶-N-氧化物在PMe 3存在下。
更新日期：2024-04-04
SiR2), a heavier congener of ketones (R2CO), are highly reactive species that are readily converted to oligomeric siloxane (O–SiR2)n. Coordination of silanones to the transition-metal fragments to afford silanone-coordinated complexes is a reliable silanone stabilization method. Recently, our group reported the synthesis, structures, and reactivity of dimesityl-substituted silanone complexes Cp*(OC)2M{OSiMes2(L)}(SiMe3) (M = W, Mo, L: Lewis base, Cp*: η5-C5Me5, Mes: 2,4,6-Me3C6H2). Herein, to investigate the effect of substituents on the silicon atom during the formation of a silanone complex, we demonstrated the use of Mes and smaller Me groups. As a result, the formation of Mes(Me)-substituted silanone molybdenum complex Cp*(OC)2Mo{OSiMes(Me)(py)}(SiMe3) (5b, py: pyridine) was suggested, the silanone tungsten complex Cp*(OC)2W{OSiMes(Me)(DMAP)}(SiMe3) (4a, DMAP: 4-(dimethylamino)pyridine) was obtained, and a dimethyl-substituted disiloxanyloxy(dioxo) complex Cp*(O)2W(OSiMe2OSiMe3) (9) was formed. The reaction of 4a with PMe3 proceeded via the elimination of DMAP and migration of the SiMe3 group to the oxygen atom of the silanone ligand to afford Cp*(OC)2W(SiMes(Me)OSiMe3)(PMe3) (11a). The Mo complex Cp*(OC)2Mo(SiMes(Me)OSiMe3)(PMe3) (11b) was produced by the reaction of Cp*(OC)2Mo{SiMes(Me)}(SiMe3) (7b) with pyridine-N-oxide in the presence of PMe3.
中文翻译：
(异三叉基)n(甲基)2−n亚甲硅烷基络合物与吡啶-N-氧化物（n = 1 和 0）的反应：形成硅烷酮络合物和二硅氧烷氧基络合物
硅烷酮 (O
SiR 2 ) 是酮 (R 2 CO )的较重同系物，是高反应性物质，很容易转化为低聚硅氧烷 (O–SiR 2 ) n。硅烷酮与过渡金属片段配位以提供硅烷酮配位络合物是一种可靠的硅烷酮稳定方法。最近，我们课题组报道了二三甲苯基取代硅酮配合物Cp*(OC) 2 M{O SiMes 2 (L)}(SiMe 3 ) (M = W, Mo, L: Lewis碱，Cp )的合成、结构及反应活性*：η 5 -C 5 Me 5、Mes：2,4,6-Me 3 C 6 H 2 )。在此，为了研究硅酮络合物形成过程中取代基对硅原子的影响，我们演示了 Mes 和更小的 Me 基团的使用。结果表明，形成了Mes(Me)取代的硅烷酮钼络合物Cp*(OC) 2 Mo{O SiMes(Me)(py)}(SiMe 3 ) ( 5b，py:吡啶)，即硅烷酮钨得到络合物Cp*(OC) 2 W{O SiMes(Me)(DMAP)}(SiMe 3 )( 4a，DMAP：4-(二甲基氨基)吡啶)，得到二甲基取代的二硅氧烷氧基(二氧代)络合物Cp*(形成O) 2 W(OSiMe 2 OSiMe 3 ) ( 9 )。 4a与 PMe 3的反应通过DMAP 的消除和 SiMe 3基团迁移至硅烷酮配体的氧原子进行，得到 Cp*(OC) 2 W(SiMes(Me)OSiMe 3 )(PMe 3 ) ( 11a）。 Mo络合物Cp*(OC) 2 Mo(SiMes(Me)OSiMe 3 )(PMe 3 ) ( 11b )是通过Cp*(OC) 2 Mo{ SiMes(Me)}(SiMe 3 ) ( 7b )反应生成的)与吡啶-N-氧化物在PMe 3存在下。
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