本篇論文研究釩的β-二酮亞胺錯合物(Nacnac)DippVCl2
((Nacnac)Dipp = HC(C(Me)N-2,6- iPr2C6H3)2)的活性。吾人嘗試在吡啶或對-二甲胺基吡啶存在的條件下來嘗試活化氮氣。可是在氮氣系統下以鉀石墨還原可得到兩個氯原子橋接兩個釩金屬的錯合物[V(NC5H5)(μ-Cl)(Nacnac)Dipp]2 (1)，及配基上的氮-碳鍵被打斷的單核釩金屬錯合物[(2,6-iPr2C6H3)NC(CH3)CHC(CH3)VN(2,6-iPr2C6H3)(N2C7H10)] (2)。
另一方面，我們也研究具有反三明治式結構的雙釩金屬錯合物(μ-η6:η6-C7H8)[V(Nacnac)Dipp]2 (3)與鄰二氮雜苯類化合物，如: 噠嗪(pyridazine)、酞嗪(phthalazine)以及3,6-二苯基-1,2,4,5-四嗪(3,6-diphenyl-1,2,4,5-tetrazine)反應可得到基質開環後與釩金屬鍵結的七員或八員環金屬環化物V(Nacnac)Dipp[NC4H4N] (4) 、V(Nacnac)Dipp(NC8H6N) (5) 及[(μ-NC(Ph)N)V(Nacnac)Dipp]2 (7)，而3與鄰二氮萘(benzo[c]cinnoline)反應生成以氮-氮鍵配位到釩金屬的錯合物(η2-benzo[c]cinnoline)2V(Nacnac) Dipp (6)
我們也對一氧化氮的活化有高度的興趣，我們合成了一價釕金屬的β-二酮亞胺錯合物[Ru(nacnac)Dmp(η6-p-cymene)](8)
((Nacnac)Dmp = HC(C(Me)NC6H3Me2)2)並研究其與過量的一氧化氮反應，在0 °C反應時可得到以反式次硝酸基橋接的雙核釕金屬錯合物(μ-κ1: κ1-O-N=N-O)[Ru(nacnac)Dmp(NO)2]2 (9)，而在室溫下與一氧化氮進行反應卻可得到一氧化氮以側接型式橋接的新穎雙核釕金屬錯合物(μ-κ2: κ2-NO)(μ-NO)[Ru(nacnac)Dmp(NO)]2 (10)。另一方面，二價的釕化合物[Ru(nacnac)Dmp(η6-p-cymene)](OTf) (11)及[Ru(nacnac)Dmp(Cl)(η6-p-cymene)]分別與過量的一氧化氮反應可收集到錯合物Ru(nacnac)Dmp(NO)2 (OTf) (12)與Ru(nacnac)Dmp(NO)Cl2 (13)
，錯合物12與13利用KC8還原皆可得到10。

In order to activate dinitrogen, reduction of the trivalent vanadium β-diketiminate (Nacnac)DippVCl2 ((Nacnac)Dipp = HC(C(Me)N-2,6- iPr2C6H3)2) by KC8 in the presence of a σ-donor, such as pyridine or 4-dimethylaminopyridine (DMAP), under dinitrogen atmosphere led to the isolation of [V(NC5H5)(μ-Cl)(Nacnac)Dipp]2 (1) with two chloro ligands bridging two vanadium atoms. Meanwhile, the imido complex [(2,6-iPr2C6H3)NC(CH3)CHC(CH3)VN(2,6-iPr2C6H3)(N2C7H10)] (2) formed via a β-diketiminato ligand degradation was also isolated.
Reactions of the univalent vanadium inverted-sandwich complex (μ-η6:η6-C7H8)[V(Nacnac)Dipp]2 (3) with diaza-containing arenes have also been investigated. Seven- and eight-membered diaza metallacycles V(Nacnac)Dipp[NC4H4N] (4), V(Nacnac)Dipp(NC8H6N) (5) and [(μ-NC(Ph)N)V(Nacnac)Dipp]2 (7) were obtained via ring opening of pyridazine, phthalazine and 3,6-diphenyl-1,2,4,5-tetrazine.
However, benzo[c]cinnoline acts as a σ-donor when reacted with 3 to give (η2-benzo[c]cinnoline)2V(Nacnac) Dipp (6).
Nitric oxide activation by Ru β-diketiminate was also investigated. Reactions of the univalent half-sandwich ruthenium complex [Ru(nacnac)Dmp(η6-p-cymene)] with an excess amount of NO at 0°C, yielded a dinuclear ruthenium complex (μ-κ1: κ1-O-N=N-O)[Ru(nacnac)Dmp(NO)2]2 (9), where two Ru centers is linked together by a hyponitrito ligand resulted from the coupling of two two NO. On the other hand, exposure of 8 to an excess amount of NO at room temperature yielded the complex (μ-κ2: κ2-NO)(μ-NO)[Ru(nacnac)Dmp(NO)]2 (10), in which two Ru atoms are bridged by one NO ligand in a remarkable side-on fashion.
Interestingly, introduction of an excess amount of NO into the Ru(II) β-diketiminate [Ru(nacnac)Dmp(η6-p-cymene)](OTf) (11) and [Ru(nacnac)Dmp(Cl)(η6-p-cymene)] (12) resulted in the formation of Ru(nacnac)Dmp(NO)2 (OTf) (12) and Ru(nacnac)Dmp(NO)Cl2 (13).
Reduction of both 12 and 13 with KC8 gave complex 10.

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