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Synthesis and Chemistry of Dihydridoborate Group 7 Metal Complexes with Varied N,E-Chelated Ligands (E = O, NH, or S)
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-12-27 , DOI: 10.1021/acs.inorgchem.2c03095 Kriti Pathak 1 , Shivankan Mishra 1 , Chandan Nandi 1 , Suvam Saha 1 , Sundargopal Ghosh 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-12-27 , DOI: 10.1021/acs.inorgchem.2c03095 Kriti Pathak 1 , Shivankan Mishra 1 , Chandan Nandi 1 , Suvam Saha 1 , Sundargopal Ghosh 1
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Several dihydridoborate group 7 metal complexes have been synthesized and their structural aspects have been described from various N,S-, N,N-, and N,O-chelated borate species, such as Na[(H3B)mp] (mp = 2-mercaptopyridyl), Na[(H3B)amt] (amt = 2-amino-5-mercapto-1,3,4-thiadiazolyl), Na[(H3B)hp] (hp = 2-hydroxypyridyl), Na[(H2B)bap] (bap = bis(2-aminopyridyl)), and Na[(H2B)bdap] (bdap = bis(2,6-diaminopyridyl)). Room temperature photolysis of [M2(CO)10] (M = Mn or Re) with these borate species afforded dihydridoborate complexes [(CO)3M(μ-H)2BHL] 1–6 (1, M = Mn, L = mp; 2, M = Re, L = mp; 3, M = Mn, L = amt; 4, M = Mn, L = hp; 5, M = Mn, L = ap; 6, M = Mn, L = dap, ap = 2-aminopyridyl, dap = 2,6-diaminopyridyl). In complexes 1–3, the corresponding (H2BHL) units are coordinated to the metal centers through the (κ3-H,H,S) mode. However, in complexes 4 and 5 (or 6), the connection is via (κ3-H,H,O) and (κ3-H,H,N) modes of coordination, respectively. Complexes 1 and 5 underwent hydroboration reactions with terminal alkynes that yielded trans-hydroborated species [Mn(CO)3(μ-H)2(NC5H4E)B(PhC═CH2)] (7, E = S; 8, E = NH). Density functional theory (DFT) calculations have been carried out to investigate the electronic structures of these dihydridoborate species as well as the nature of bonding in them.
中文翻译：
具有不同 N,E-螯合配体（E = O、NH 或 S）的第 7 族二氢硼酸盐金属配合物的合成和化学
已经合成了几种二氢硼酸盐第 7 族金属络合物，并且已经从各种 N,S-、N,N- 和 N,O- 螯合硼酸盐物种（例如 Na[(H 3 B)mp] (mp = 2-巯基吡啶基), Na[(H 3 B)amt] (amt = 2-amino-5-mercapto-1,3,4-thiadiazolyl), Na[(H 3 B)hp] (hp = 2-hydroxypyridyl )、Na[(H 2 B)bap] (bap = bis(2-aminopyridyl)) 和 Na[(H 2 B)bdap] (bdap = bis(2,6-diaminopyridyl))。[M 2 (CO) 10 ]（M = Mn 或 Re）与这些硼酸盐物质的室温光解得到二氢硼酸盐络合物 [(CO) 3 M(μ-H) 2 BHL] 1 – 6 (1、M=Mn，L=mp；2、M=Re，L=mp；3、M=Mn，L=amt；4、M=Mn，L=hp；5、M=Mn，L=ap；6 , M = Mn, L = dap, ap = 2-氨基吡啶基, dap = 2,6-二氨基吡啶基)。在配合物1 – 3中，相应的 (H 2 BHL) 单元通过 (κ 3 -H,H,S) 模式与金属中心配位。然而，在配合物4和5（或6）中，连接分别通过 (κ 3 -H,H,O) 和 (κ 3 -H,H,N) 配位模式。配合物1和5与末端炔烃进行硼氢化反应，产生反式硼氢化物质 [Mn(CO) 3 (μ-H) 2 (NC 5 H 4 E)B(PhC =CH 2 )] ( 7 , E = S; 8 , E =新罕布什尔州）。已经进行密度泛函理论 (DFT) 计算以研究这些二氢硼酸盐物种的电子结构以及它们中的键合性质。
更新日期：2022-12-27
中文翻译：
具有不同 N,E-螯合配体（E = O、NH 或 S）的第 7 族二氢硼酸盐金属配合物的合成和化学
已经合成了几种二氢硼酸盐第 7 族金属络合物，并且已经从各种 N,S-、N,N- 和 N,O- 螯合硼酸盐物种（例如 Na[(H 3 B)mp] (mp = 2-巯基吡啶基), Na[(H 3 B)amt] (amt = 2-amino-5-mercapto-1,3,4-thiadiazolyl), Na[(H 3 B)hp] (hp = 2-hydroxypyridyl )、Na[(H 2 B)bap] (bap = bis(2-aminopyridyl)) 和 Na[(H 2 B)bdap] (bdap = bis(2,6-diaminopyridyl))。[M 2 (CO) 10 ]（M = Mn 或 Re）与这些硼酸盐物质的室温光解得到二氢硼酸盐络合物 [(CO) 3 M(μ-H) 2 BHL] 1 – 6 (1、M=Mn，L=mp；2、M=Re，L=mp；3、M=Mn，L=amt；4、M=Mn，L=hp；5、M=Mn，L=ap；6 , M = Mn, L = dap, ap = 2-氨基吡啶基, dap = 2,6-二氨基吡啶基)。在配合物1 – 3中，相应的 (H 2 BHL) 单元通过 (κ 3 -H,H,S) 模式与金属中心配位。然而，在配合物4和5（或6）中，连接分别通过 (κ 3 -H,H,O) 和 (κ 3 -H,H,N) 配位模式。配合物1和5与末端炔烃进行硼氢化反应，产生反式硼氢化物质 [Mn(CO) 3 (μ-H) 2 (NC 5 H 4 E)B(PhC =CH 2 )] ( 7 , E = S; 8 , E =新罕布什尔州）。已经进行密度泛函理论 (DFT) 计算以研究这些二氢硼酸盐物种的电子结构以及它们中的键合性质。
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