Murphy Brendan L, Gabbaï François P
Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, United States.
Organometallics. 2025 Aug 5;44(16):1751-1755. doi: 10.1021/acs.organomet.5c00229. eCollection 2025 Aug 25.
Intramolecular Lewis adducts, especially those bearing a boron Lewis acid and a phosphine oxide Lewis base, have become attractive motifs for tunable luminescence properties in materials. However, intramolecular Lewis adducts with Ch-(IV)O moieties (Ch = chalcogen) as Lewis bases are under-represented in the field. Here, we describe the syntheses of two chalcogen boranes of general formula -(PhCh)-(BMes)-CH (Ch = S (), Se ()) and their conversions into the corresponding chalcogen-oxide boranes of general formula -(PhChO)-(BMes)-CH (Ch = S (), Se ()). While both and form inner adducts held by ChO→B dative bonds in the solid state and in solution, we examine the bistabilities of these interactions computationally and experimentally. Interestingly, the reaction of and HF·pyridine gives rise to -(SePhMes)-(BF)-CH () which shows evidence for F→Se intramolecular chalcogen bonding.
分子内路易斯加合物，特别是那些含有硼路易斯酸和氧化膦路易斯碱的加合物，已成为材料中可调谐发光性质的有吸引力的结构单元。然而，以Ch-(IV)O部分（Ch = 硫族元素）作为路易斯碱的分子内路易斯加合物在该领域的研究较少。在此，我们描述了通式为-(PhCh)-(BMes)-CH（Ch = S ()，Se ()）的两种硫族硼烷的合成及其向通式为-(PhChO)-(BMes)-CH（Ch = S ()，Se ()）的相应硫族氧化物硼烷的转化。虽然 和 在固态和溶液中均形成由ChO→B配位键维系的内加合物，但我们通过计算和实验研究了这些相互作用的双稳态。有趣的是， 和HF·吡啶的反应生成了-(SePhMes)-(BF)-CH ()，其显示出F→Se分子内硫族键的证据。
