5 years ago

Design, Synthesis, and Chemistry of Bis(σ)borate and Agostic Complexes of Group 7 Metals

Design, Synthesis, and Chemistry of Bis(σ)borate and Agostic Complexes of Group 7 Metals
Thierry Roisnel, Kriti Pathak, Sundargopal Ghosh, Vincent Dorcet, Jean-François Halet, Rongala Ramalakshmi, Koushik Saha, Suman Gomosta
A series of new bis(σ)borate and agostic complexes of group 7 metals have been synthesized and structurally characterized from various borate ligands, such as trihydrobis(benzothiazol-2-yl)amideborate (Na[(H3B)bbza]), trihydro(2-aminobenzothiazolyl)borate (Na[(H3B)abz]), and dihydrobis(2-mercaptopyridyl)borate (Na[(H2B)mp2]) (bbza=bis(benzothiazol-2-yl)amine, abz=2-aminobenzothiazolyl, and mp=2-mercaptopyridyl). Photolysis of [Mn2(CO)10] with Na[(H3B)bbza] formed bis(σ)borate complex [Mn(CO)3(μ-H)2BHNCSC6H4(NR)] (1; R=NCSC6H4). Octahedral complex [Re(CO)2(N3C2S2C12H8)2] (2) was generated under similar reaction conditions with [Re2(CO)10]. Similarly, when [Mn2(CO)10] was treated with Na[(H3B)abz], bis(σ)borate complex [Mn(CO)3(μ-H)2BH(HN2CSC6H4)] (3) and the agostic complex [Mn(CO)3(μ-H)BH(HN2CSC6H4)2] (4) were formed. To probe the potential formation of agostic complexes of the heavier group 7 metals, we carried out the photolysis of [M2(CO)10] with Na[(H2B)mp2] and found that [M(CO)3(μ-H)BH(C5H4NS)2] (5: M=Re; 6: M=Mn) was formed in moderate yield. Complexes 1 and 3 feature a (κ3-H,H,N) coordination mode, whereas 4, 5, and 6 display both (κ3-H,N,N) and (κ3-H,S,S) modes of the corresponding ligands. To investigate the lability of the CO ligands of 1 and 3, we treated the complexes with phosphine ligands that generated novel bis(σ)borate complexes [Mn(μ-H)2(BHNCSC6H4)(NR)(CO)2PL2L’] (R=NCSC6H4; 7 a: L=L’=Ph; 7 b: L=Ph, L’=Me) and [Mn(μ-H)2BHN(NCSC6H4)R(CO)2PL2L’] (R=NCSC6H4; 8 a: L=L’=Ph; 8 b: L=Ph, L’=Me). Complexes 7 and 8 are structural isomers with different coordination modes of the bbza ligand. In addition, DFT calculations were performed to shed some light on the bonding and electronic structures of these complexes. Let it B: Several borate ligands with group 7 metals that show novel structures, bonding, and reactivities were synthesized. In addition, some bis(σ)borate complexes reacted with phosphines and led to the isolation of isomeric borate complexes (see scheme).

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201701423

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