tetra-n-butylammonium nitridoosmate(VIII)

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: tetra-n-butylammonium nitridoosmate(VIII)
• 英文别名: Azanylidyne-oxido-dioxoosmium;tetrabutylazanium
• 化学式: C₁₆H₃₆N*NO₃Os
• 分子量: 494.673
• InChiKey: IUSYSLKWJKAGAZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.59
• 重原子数：
  22
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  81
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tetra-n-butylammonium nitridoosmate(VIII) 、 Rh(cod)(tos)(H2O) 以 丙酮 为溶剂， 以70%的产率得到
  参考文献：
  名称：

  Syntheses and crystal structures of bi- and tri-metallic complexes containing a trioxoosmium(VIII) moiety

  摘要：

  与[NBu₄][NOsO₃]的相互作用生成了双金属氮桥复合物：cis-[Pt(dppm)(NOsO₃)₂] 3、trans-[Pt(Bupy)₂(NOsO₃)₂] 4、[Ir(CO)(PPh₃)₂(NO₃Os)] 5和[{Rh(cod)(NOsO₃)}₂] 6。复合物4结晶于P空间群，a = 7.936(1)，b = 10.758(2)，c = 7.738(1) Å，α = 100.02(1)，β = 99.75(1)，γ = 101.75(1)°，U = 622.5(2) ų，Z = 1。Pt–N (Os)、Os–N和平均Os–O距离分别为1.958(7)、1.681(7)和1.724 Å。复合物5结晶于P2₁/n空间群，a = 10.124(1)，b = 15.564(2)，c = 22.623(3) Å，β = 100.08(2)°，U = 3509.7(7) ų，Z = 4。Ir–N、Os–N和平均Os–O距离分别为1.998(7)、1.710(7)和1.718 Å。将[Au(PPh₃)(NOsO₃)] 1与Ph₃PNPh处理生成N-膦亚胺复合物[Au(PPh₃){N(PPh₃)Ph}][NOsO₃] 7。复合物7结晶于P2₁/n空间群，a = 8.780(1)，b = 20.781(2)，c = 20.711(5) Å，β = 91.23(1)°，U = 3788.0(9) ų，Z = 4。Au–N距离为2.091(8) Å，磷亚胺中的C–N–P角度为127.0(7)°。将1与Bupy反应导致Bupy替代[NOsO₃]并形成[Au(PPh₃)(Bupy)][NOsO₃] 8。将[Pt(dppf)(O₃SCF₃)Cl]（dppf = 1,1'-双（苯基膦基）铁烷）与[NBu₄][NOsO₃]反应生成三金属复合物[Pt(dppf)(NOsO₃)Cl] 11。复合物11结晶于P2₁/c空间群，a = 20.058(2)，b = 14.899(1)，c = 23.949(2) Å，β = 114.57(2)°，U = 6508(1) ų，Z = 8。平均Pt–N、Os–N和Os–O距离分别为2.06、1.66和1.67 Å。

  DOI：

  10.1039/a702404e
• 作为产物：
  描述：

  (T-4)-氮三氧代-锇酸钾 、 四丁基氯化铵 生成 tetra-n-butylammonium nitridoosmate(VIII)
  参考文献：
  名称：

  Miskowski, V.; Gray, H. B.; Poon, C. K., Molecular Physics, 1974, vol. 28, p. 747 - 757

  摘要：

  DOI：
• 作为试剂：
  描述：

  2,2-二甲基丁烷 在 tetra-n-butylammonium nitridoosmate(VIII) 、 三氯化铁 作用下， 以 二氯甲烷 、 溶剂黄146 为溶剂， 反应 0.01h， 以35%的产率得到频哪酮
  参考文献：
  名称：

  FeCl₃-Activated Oxidation of Alkanes by [Os(N)O₃]^-

  摘要：

  Although the ion [Os-VIII(N)(O)(3)](-) is a stable species and is not known to act as an oxidant for organic substrates, it is readily activated by FeCl3 in CH2Cl2/CH3CO2H to oxidize alkanes efficiently at room temperature. The oxidation can be made catalytic by using 2,6-dichloropyridine N-oxide as the terminal oxidant. The active intermediates in stoichiometric and catalytic oxidation are proposed to be [(O)(3)Os(VIII)dropN-Fe-III] and [Cl-4(O)Os(VIII)dropN-Fe-III], respectively.

  DOI：

  10.1021/ja0487832

文献信息

• Dioxo- and nitrido-osmium complexes with imidodiphosphinochalcogenido ligands [N(QPR2)2]− (Q = S or Se; R = Ph or Pri)
  作者：Qian-Feng Zhang、Kwok-Kin Lau、Joyce L. C. Chim、Terry K. T. Wong、Wing-Tak Wong、Ian D. Williams、Wa-Hung Leung

  DOI：10.1039/b003798m

  日期：——

  trans-K2[OsVIO2(OH)4] with 2 equivalents of HN(QPR2)2 yielded the dioxoosmium(VI) complexes trans-[OsO2N(QPR2)2}2] (Q = S, R = Ph 1 or Pri2; Q = Se, R = Ph 3). Complexes 1–3 have been characterised by X-ray crystallography. The Os–O distances in 1–3 are 1.739, 1.734 and 1.748 Å, respectively. trans-[OsNN(QPR2)2}2Cl] (R = Pri, Q = S; R = Ph, Q = Se) were obtained by reactions of [NBu4n][OsNCl4] with K[N(QPR2)2]

  的反应反式-K 2 [O的VI ø 2（OH）4 ]与2个当量的HN（QPR的2）2，产生dioxoOSmium（VI）络合物的反式- [的OSO 2 N（QPR 2）2 } 2 ]（Q = S，R =苯基1或Pr我2 ; Q =硒，R =苯基3）。配合物1-3具有以下特征：X射线晶体学。1-3中的OS-O距离分别为1.739、1.734和1.748Å。反式-[OSN N（QPR 2）2 } 2 Cl]（R = Pr i，Q = S; R = Ph，Q = Se）通过[NBu 4 n ] [OSNCl 4 ]与K [ N（QPR 2）2 ]。用[NBu 4 n ] [OSO 3 N]处理[OSN N（SPPh 2）2 } 2 ] [BF 4 ]导致形成μ- nitrido OS VIII -OS VI复合物[OSN N（SPPh）2） 2 } 2（NOSO 3）]，其中，[NOSO
• Dimetallic gold(I) and platinum(II) complexes containing a trioxoosmium(VIII) moiety. Crystal structures of [Au(PPh3)(NOsO3)] and cis-[Pt(PMe3)2(NOsO3)2]
  作者：Wa-Hung Leung、Joyce L. C. Chim、Wing-Tak Wong

  DOI：10.1039/dt9960003153

  日期：——

  Reaction of [NBun4][OsO3N] with [Au(PPh3)(CF3SO3)] and cis-[Pt(PMe3)2(CF3SO3)2] afforded the dimetallic complexes [Au(PPh3)(NOsO3)] and cis-[Pt(PMe3)2(NOsO3)2], respectively, which have been characterised by X-ray crystallography.

  [NBun4][OsO3N] 与 [Au(PPh3)(CF3SO3)] 和 cis-[Pt(PMe3)2(CF3SO3)2] 反应得到双金属配合物 [Au(PPh3)(NOsO3)] 和 cis-[Pt (PMe3)2(NOsO3)2]分别通过X射线晶体学进行了表征。
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Os: SVol.1, 4.2.1.1.1.1, page 208 - 209
  作者：

  DOI：——

  日期：——
• Heterobimetallic μ-nitrido complexes containing ruthenium(II) dithiocarbamate
  作者：Hegen Zheng、Wa-Hung Leung、Joyce L.C Chim、Willetta Lai、Chong-Ho Lam、Ian D Williams、Wing-Tak Wong

  DOI：10.1016/s0020-1693(00)00169-9

  日期：2000.8

  Interaction of [Ru(Co)H(Et(2)dtc) with triflic acid (HOTf) afforded [Ru(Co)H(Et(2)dtc)(PPh3)(2)(OTf) (1), which has been characterized by X-ray crystallography. The Ru-C, Ru-O, average Ru-S and average Ru-P distances in 1 an 1.811(5), 2.216(3), 2.433 and 2.423 Angstrom, respectively. Reaction of 1 with amines L results in the formation of adducts trans-[Ru(CO)(Et(2)dtc)(PPh3)(2)L](OTf) (L = N2H4 (2) and NH2OH (3)). The Ru-C, Ru-N, average Ru-S and average Ru-P distance in 3 are 1.85(1), 2.179(8), 2.433 and 2.393, respectively; the Ru-N-O angle being 119.7(5)degrees. Treatment of 1 with [(NBu4)-Bu-n][OsN(C7H6S2)(2)] ([C7H6S2](2-) =3,4-toluenedithiolate(2-)), and [ReN(Et(2)dtc)(2)] (Et(2)dtc = N,N-diethyldithiocarbamate) gave the corresponding mu-nitrido complexes [Ru(CO)(Et(2)dtc)(PPh3)(2)(NOsO3)] (4), [Ru(CO)(Et(2)dtc)(PPh3)(2)NOs(C7H6S2)(2)}] (5) and [Ru(CO)(Et(2)dtc)(PPh3)(2)NRe(Et(2)dtc)(2)}] (6). The structures of complexes 4-6 have been established by X-ray crystallography. The Os-N and Ru-N distances, and Os-N-Ru angle in 4 are 1.719(7) and 2.075(7) Angstrom, and 155.1(4)degrees, respectively. The Os-N and Ru-N distances and Os-N-Ru angle in 5 are 1.680(6) and 2.068(6) Angstrom, and 166.2(3)degrees, respectively. The Re-N and Ru-N distances, and Re-N-Ru angle for 6 are 1.670(3) and 2.108(3) Angstrom, and 170.9(2)degrees, respectively. The bond lengths and angles for these mu-nitrido complexes are indicative of asymmetric bridging mode of nitride, i.e. M=N --> Ru(II) (M = Os(VIII), Os(VI), Re(V)). (C) 2000 Elsevier Science S.A. All rights reserved.
• Heterobimetallic nitrido-bridged Ru(II)NOs(VIII) and Ru(II)NOs(VI) complexes containing ruthenium porphyrins
  作者：Wa-Hung Leung、Joyce L.C. Chim、Willetta Lai、Leo Lam、Wing-Tak Wong、Wing Hang Chan、Chi-Hung Yeung

  DOI：10.1016/s0020-1693(99)00096-1

  日期：1999.6

  Treatment of Ru(por)(NO)(OTf) (por=dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin H-2(OEP) or 5,10,15,20-tetra(p-tolyl)porphyrin H-2(TTP), OTf=triflate) with [(NBu4)-Bu-n][OsO3N] afforded the nitrido-bridged Ru(II)-Os(VIII) complexes [(por)(NO)RuNOsO3] (por=OEP (3) or TTP (4)). The structure of 3 has been established by X-ray crystallography. The Ru-N(O), Ru-N(Os and Os-N distances in 3 are 1.83(2, 2.03(1) and 1.79(1) Angstrom, respectively; the Ru-N-O and Ru-N-Os angles are 153(1) and 138.4(8)degrees, respectively. Reaction of Ru(por)(NO)(OTf) with [(NBu4)-Bu-n]OsNL2] (H2L = 3,4-toluenedithiol) gave the nitrido-bridged Ru(II)-Os(VI) complexes (por)(NO)RuNOsL2 (por = OEP (5), TTP (6)). Treatment of Ru(OEP)(NO)(OTf) with ReN(Et(2)dtc)(2) (Et(2)dtc = N,N-diethyldithiocarbamate) afforded the Ru(IT)-Re(V) complex (OEP)(NO)RuNRe(Et(2)dtc)(2)(OTf) (7). Complexes 3 and 4 exhibit porphyrin-centered oxidation along with Os(VIII)-Os(VIT) and Ru(II)-Ru(I) reductions. Complexes 5 and 6 exhibit Os(VII)-Os(VI) and porphyrin ring oxidation along with Ru(II)-Ru(I) reduction. (C) 1999 Elsevier Science S.A. All rights reserved.