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Electrospray Ionization Tandem Mass Spectrometry and DFT Survey of Copper(I) Ate Complexes Containing Coordinated Borohydride Anions
ACS Environmental Au Pub Date : 2022-06-24 , DOI: 10.1021/jasms.2c00103 Howard Z Ma 1 , Allan J Canty 2 , Richard A J O'Hair 1
ACS Environmental Au Pub Date : 2022-06-24 , DOI: 10.1021/jasms.2c00103 Howard Z Ma 1 , Allan J Canty 2 , Richard A J O'Hair 1
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Copper(I) borohydride ate complexes of the type Cat+[XCu(BH4)]− have been previously postulated as intermediates in the reactions of copper salts with borohydride. Negative ion electrospray ionization of an acetonitrile solution of copper(I) phenylacetylide with a 10-fold excess of sodium borohydride (NaBH4) revealed the formation of a diverse range of mononuclear, dinuclear and trinuclear cuprates with different numbers of BH4–, H– and CN– ligands, the latter likely being formed by abstraction of CN– from the acetonitrile solvent. Collision-induced dissociation was used to examine the fragmentation reactions of the following borohydride containing cuprates: [Cu(H)(BH4)]−, [Cu(BH4)2]−, [Cu(BH4)(CN)]−, [Cu2(H)(BH4)2]−, [Cu2(H)2(BH4)]−, [Cu2(BH4)2(CN)]−, [Cu2(H)(BH4)(CN)]−, [Cu3(H)(BH4)3]−, [Cu3(H)2(BH4)2]−, [Cu3(H)3(BH4)]−, [Cu3(BH4)2(CN)2]−, and [Cu3(H)(BH4)2(CN)]−. In all cases, BH3 loss is observed. For many of the dinuclear and trinuclear complexes cluster fragmentation by loss of CuH was also observed. In the case of [Cu2(H)2(BH4)]− and [Cu3(H)3(BH4)]−, loss of H2 was also observed. DFT calculations were used to explore potential structures of the various borohydride-containing cuprates and to predict the overall reaction energetics for the various fragmentation channels.
中文翻译：
含有配位硼氢化物阴离子的铜 (I) 配合物的电喷雾电离串联质谱和 DFT 调查
Cat + [XCu(BH 4 )] -类型的硼氢化铜 (I) 配合物先前已被假定为铜盐与硼氢化物反应的中间体。用 10 倍过量的硼氢化钠 (NaBH 4 )对苯乙炔铜 (I) 的乙腈溶液进行负离子电喷雾电离，结果表明形成了具有不同数量 BH 4 –、H的各种单核、双核和三核铜酸盐–和 CN –配体，后者很可能是通过提取 CN 形成的–来自乙腈溶剂。碰撞诱导解离用于检查以下含硼氢化物的铜酸盐的碎裂反应：[Cu(H)(BH 4 )] - , [Cu(BH 4 ) 2 ] - , [Cu(BH 4 )(CN)] - , [Cu 2 (H)(BH 4 ) 2 ] - , [Cu 2 (H) 2 (BH 4 )] - , [Cu 2 (BH 4 ) 2 (CN)] - , [Cu 2 (H) (BH 4 )(CN)] -, [Cu 3 (H)(BH 4 ) 3 ] - , [Cu 3 (H) 2 (BH 4 ) 2 ] - , [Cu 3 (H) 3 (BH 4 )] - , [Cu 3 (BH 4 ) ) 2 (CN) 2 ] -和[Cu 3 (H)(BH 4 ) 2 (CN)] -。在所有情况下，BH 3观察到损失。对于许多双核和三核复合物，也观察到由于失去 CuH 而导致的簇碎裂。在[Cu 2 (H) 2 (BH 4 )] -和[Cu 3 (H) 3 (BH 4 )] -的情况下，也观察到H 2的损失。DFT 计算用于探索各种含硼氢化物的铜酸盐的潜在结构，并预测各种碎裂通道的整体反应能量。
更新日期：2022-06-24
中文翻译：
含有配位硼氢化物阴离子的铜 (I) 配合物的电喷雾电离串联质谱和 DFT 调查
Cat + [XCu(BH 4 )] -类型的硼氢化铜 (I) 配合物先前已被假定为铜盐与硼氢化物反应的中间体。用 10 倍过量的硼氢化钠 (NaBH 4 )对苯乙炔铜 (I) 的乙腈溶液进行负离子电喷雾电离，结果表明形成了具有不同数量 BH 4 –、H的各种单核、双核和三核铜酸盐–和 CN –配体，后者很可能是通过提取 CN 形成的–来自乙腈溶剂。碰撞诱导解离用于检查以下含硼氢化物的铜酸盐的碎裂反应：[Cu(H)(BH 4 )] - , [Cu(BH 4 ) 2 ] - , [Cu(BH 4 )(CN)] - , [Cu 2 (H)(BH 4 ) 2 ] - , [Cu 2 (H) 2 (BH 4 )] - , [Cu 2 (BH 4 ) 2 (CN)] - , [Cu 2 (H) (BH 4 )(CN)] -, [Cu 3 (H)(BH 4 ) 3 ] - , [Cu 3 (H) 2 (BH 4 ) 2 ] - , [Cu 3 (H) 3 (BH 4 )] - , [Cu 3 (BH 4 ) ) 2 (CN) 2 ] -和[Cu 3 (H)(BH 4 ) 2 (CN)] -。在所有情况下，BH 3观察到损失。对于许多双核和三核复合物，也观察到由于失去 CuH 而导致的簇碎裂。在[Cu 2 (H) 2 (BH 4 )] -和[Cu 3 (H) 3 (BH 4 )] -的情况下，也观察到H 2的损失。DFT 计算用于探索各种含硼氢化物的铜酸盐的潜在结构，并预测各种碎裂通道的整体反应能量。
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