carbonylosmium(II) 2,3,7,8,12,13,17,18-octaethylporphyrinate | 77244-32-7

• 英文名称: carbonylosmium(II) 2,3,7,8,12,13,17,18-octaethylporphyrinate
• 英文别名: (2,3,7,8,12,13,17,18-octaethylporphyrinato)Os(CO)；[(2,3,7,8,12,13,17,18-octaethylporphyrinato)Os(CO)]；[Os(2,3,7,8,12,13,17,18-octaethylporphyrinato)(CO)]；(octaethylporphyrinato)Os(CO)；Os(octaethylporphyrinato)(CO)；(OEP)Os(CO)
• CAS: 77244-32-7
• 化学式: C₃₇H₄₄N₄OOs
• 分子量: 750.983
• InChiKey: PGQSQMFCGNEDRB-RZBSDYLMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  carbonylosmium(II) 2,3,7,8,12,13,17,18-octaethylporphyrinate 在 甲醇 、 氧气 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 以70%的产率得到μ-oxo bis(methoxooctaethylporphyrinatoosmium(IV))
  参考文献：
  名称：

  SYNTHESIS AND CHARACTERIZATION OF μ-OXO BIS(METHOXOOCTAETHYLPORPHYRINATOOSMIUM(IV))

  摘要：

  用 2,3 二甲基吲哚/O2 氧化八乙基卟啉锇（II）羰基，得到了一种新的四价锇配合物。元素分析、分子量测量和光谱数据表明，该络合物是八乙基卟啉锇（IV）甲氧化物的双磁性线性 μ-oxo 二聚体；[OEPOs(IV)OCH3]2O。

  DOI：

  10.1246/cl.1981.297
• 作为产物：
  描述：

  Os(III) (2,3,7,8,12,13,17,18-octaethylporphyrinate)(CO)(Cl) 在 tin(ll) chloride 作用下， 以 二氯甲烷 为溶剂， 以>99的产率得到carbonylosmium(II) 2,3,7,8,12,13,17,18-octaethylporphyrinate
  参考文献：
  名称：

  Mosseri, Shlomo; Neta, Pedatsur; Hambright, Peter, Journal of the Chemical Society, Dalton Transactions, 1988, p. 2705 - 2712

  摘要：

  DOI：

文献信息

• Synthesis and Characterization of Osmium Nitrosyl Porphyrins Containing Organo, Halogeno, and μ-Oxo Ligands, and Extensions to the First Organometallic Thionitrosyl Porphyrin
  作者：Lin Cheng、Li Chen、Hee-Sun Chung、Masood A. Khan、George B. Richter-Addo、Victor G. Young

  DOI：10.1021/om980197s

  日期：1998.8.1

  of the complexes (in CH2Cl2) decrease in the order (OEP)Os(NO)X (1799−1795 cm-1) > [(OEP)Os(NO)]2(μ-O) (1770 cm-1) > (OEP)Os(NO)R (1748−1703 cm-1). The δmeso peaks in the 1H NMR spectra of the (OEP)Os complexes (in CDCl3) also decrease in the order (OEP)Os(NO)X (10.41−10.40 ppm) > [(OEP)Os(NO)]2(μ-O) (10.35 ppm) > (OEP)Os(NO)R (10.24−10.21 ppm) > (OEP)Os(R)2 (9.71−9.03 ppm). The thionitrosyl (OEP)Os(NS)Cl

  （OEP）OS（CO）与NOPF 6（在CH 2 Cl 2中）继之以RMgX（在THF中）的顺序反应给出了新的（OEP）OS（NO）R（5-44％）的可变分离产率， （OEP）OS（R）2（1-10％），（OEP）OS（NO）X（14-19％）和[（OEP）OS（NO）] 2（μ-O）（最多24 ％）化合物，具体取决于反应条件以及R和X的性质（OEP =八乙基卟啉对二阴离子； R = Me，Et，iPR，ŤBu，p -C 6 H 4 F；X ＝ Cl，Br）。υ的IR NO络合物的值（在CH 2氯2的顺序）减少（OEP）锇（NO）X（1799年至1795年厘米- 1）> [（OEP）OS（NO）] 2（μ-O ）（1770 cm - 1）>（OEP）OS（NO）R（1748−1703 cm - 1）。（OEP）OS配合物（在CDCl 3中）的1 H NMR光谱中的δ介观峰也以（OEP）OS（NO）X（10
• Synthesis, characterization, and protonation of octaethylporphyrin osmium nitrosyl complexes containing axial thiolate ligands - X-ray structures of an alkyl thionitrite (RSNO) and its (OEP)Os(NO)(SR) addition product
  作者：Jonghyuk Lee、Geun-Bae Yi、Douglas R Powell、Masood A Khan、George B Richter-Addo

  DOI：10.1139/v00-168

  日期：2001.5.1

  The (OEP)Os(NO)(SR) compounds (R = Me, Et, i-Pr, t-Bu) have been prepared in 33-48% isolated yields by the formal trans-addition of the precursor alkyl thionitrites (RSNO) across the metal center in (OEP)Os(CO). The nitrosyl thiolate compounds have been characterized by IR,¹H NMR, and UV-vis spectroscopy, and by FAB mass spectrometry. Their IR spectra display bands in the 1751-1755 cm^-1(KBr) range, which is indicative of terminal N-bound NO ligands in this class of compounds. The thiolate-thiol (OEP)Os(NO)(SCH₂CH₂SH) complex has been prepared in 70% isolated yield from the reaction of (OEP)Os(NO)(O-i-C₅H₁₁) with ethane-1,2-dithiol. Nitrosation of the free -SH group in (OEP)Os(NO)(SCH₂CH₂SH) with t-BuONO, followed by reaction with (TTP)Ru(CO) gave [(OEP)Os(NO)](µ-SCH₂CH₂S-S,S')[Ru(NO)(TTP)] in 70% yield by¹H NMR spectroscopy. The (OEP)Os(NO)(SCR'₂CH₂NHC(O)Me) compounds have also been prepared either by an alkoxide-thiolate exchange reaction (for R' = H) or by RSNO addition to (OEP)Os(CO) (for R' = Me). The solid-state molecular structures of the precursor RSNO thionitrite (for R' = Me) and the metalloderivative have been determined by single-crystal X-ray crystallography. Protonation of these (OEP)Os(NO)(SCR'₂CH₂NHC(O)Me) complexes gave the amide-bound [(OEP)Os(NO)(O=C(Me)NHCH₂CR'₂SH)]BF₄derivatives. The latter cationic compounds were also obtained by the sequential reaction of (OEP)Os(CO) with nitrosonium tetrafluoroborate, followed by addition of the amide-thiol reagent. Key words: thionitrite, nitrosothiol, porphyrin, X-ray structure, nitric oxide, osmium.

  (OEP)Os(NO)(SR)化合物（其中R = 甲基，乙基，异丙基，叔丁基）通过前体烷基硫亚硝酸酯（RSNO）在（OEP）Os(CO)金属中心上的形式转加反应，以33-48%的分离收率制备。这些亚硝基硫醇酸盐化合物已通过红外光谱，¹H核磁共振，紫外-可见光谱和FAB质谱进行表征。它们的红外光谱显示在1751-1755 cm^-1（KBr）范围内的吸收峰，表明这类化合物中存在末端N-配位的NO配体。通过（OEP）Os(NO)(O-i-C₅H₁₁)与乙烷-1,2-二硫醇反应，已以70%的分离收率制备了硫醇-硫醇（OEP）Os(NO)(SCH₂CH₂SH)配合物。通过¹H核磁共振光谱，用t-BuONO硝化（OEP）Os(NO)(SCH₂CH₂SH)中的自由-SH基团，然后与（TTP）Ru(CO)反应，得到了[(OEP)Os(NO)](µ-SCH₂CH₂S-S,S')[Ru(NO)(TTP)]，收率为70%。还通过烷氧基-硫醇酸盐交换反应（对于R' = H）或RSNO加成到（OEP）Os(CO)（对于R' = Me）制备了（OEP）Os(NO)(SCR'₂CH₂NHC(O)Me)化合物。通过单晶X射线衍射确定了前体RSNO硫亚硝酸酯（对于R' = Me）和金属衍生物的固态分子结构。这些（OEP）Os(NO)(SCR'₂CH₂NHC(O)Me)配合物的质子化产生了酰胺配位的[(OEP)Os(NO)(O=C(Me)NHCH₂CR'₂SH)]BF₄衍生物。后者阳离子化合物也可通过（OEP）Os(CO)与四氟硼酸亚硝酰盐的顺序反应，然后加入酰胺-硫醇试剂获得。关键词：硫亚硝酸酯，亚硝基硫醇，卟啉，X射线结构，一氧化氮，锇。
• Synthesis, characterization, and molecular structures of nitrosyl nitrito complexes of osmium porphyrins: Disproportionation of nitric oxide in its reaction with Os(P)(CO) (P = porphyrinato dianion)
  作者：Felipe A Leal、Ivan M Lorkovic、Peter C Ford、Jonghyuk Lee、Li Chen、Lindsey Torres、Masood A Khan、George B Richter-Addo

  DOI：10.1139/v03-091

  日期：2003.7.1

  The Os(P)(NO)(ONO) compounds (P = TTP, TMP, OEP, TmTP; TTP = 5,10,15,20-tetra-p-tolylporphyrinato dianion, TMP = 5,10,15,20-tetramesitylporphyrinato dianion, OEP = octaethylporphyrinato dianion, TmTP = tetra(m-tolyl)porphyrinato dianion) have been prepared from the reaction of the precursor carbonyl complexes Os(P)(CO) with excess nitric oxide. Nitrous oxide was detected as a by-product of the reaction

  Os(P)(NO)(ONO)化合物（P = TTP、TMP、OEP、TmTP；TTP = 5,10,15,20-四对甲苯基卟啉二价阴离子，TMP = 5,10,15,20-四甲基卟啉二价阴离子，OEP = 八乙基卟啉二价阴离子，TmTP = 四（间甲苯基）卟啉二价阴离子）是通过前体羰基配合物 Os（P）（CO）与过量一氧化氮的反应制备的。检测到一氧化二氮作为反应的副产物。Os(P)(NO)(ONO) 化合物（作为 KBr 颗粒）的 IR 光谱揭示了 1790??1804 cm??1 范围内的谱带，这些谱带属于 υNO。红外光谱还揭示了每个复合物在 1495??1531 和 913??962 cm??1 范围内的两个新谱带，表明 O-结合亚硝基配体。在 TTP 和 TMP 衍生物的单晶 X 射线晶体结构中，结合的 NO 基团的线性和 Os(P)(NO)(ONO) 复合物中反式亚硝基配体的 O
• Catalysed epoxidation and hydroxylation of alkene by osmium(<scp>III</scp>)–porphyrin complexes
  作者：Chi-Ming Che、Wai-Cheung Chung

  DOI：10.1039/c39860000386

  日期：——

  Osmium(III)–porphyrin complexes have been prepared by Br2 oxidation of OsII(P)(PBun3)(CO) in CH2Cl2[H2P = H2OEP (octaethylporphyrin) and H2TPP (meso-tetraphenylporphyrin)]; the ‘OsIII(P)(PBun3)Br + PhlO’ system is capable of performing epoxidation and hydroxylation of systene and cyclohexene.

  Br （III）-卟啉配合物是通过在CH 2 Cl 2 [H 2 P = H 2 OEP（八乙基卟啉）和H 2 TPP（meso ）中的Os II（P）（PBu n 3）（CO）的Br 2氧化制备的。-四苯基卟啉）]; “ Os III（P）（PBu n 3）Br + PhlO”系统能够进行烯和环己烯的环氧化和羟基化反应。
• Nitrosylation of Octaethylporphyrin Osmium Complexes with Alkyl Nitrites and Thionitrites:  Molecular Structures of Three Osmium Porphyrin Derivatives
  作者：Li Chen、Masood A. Khan、George B. Richter-Addo

  DOI：10.1021/ic9708576

  日期：1998.2.1

  (OEP)Os(CO) reacts with n-butyl nitrite to give, after workup, the (OEP)Os(NO)(O-n-Bu) trans addition product (OEP = octaethylporphyrinato dianion). Similarly, the reaction of (OEP)Os(CO) or [(OEP)Os](2) with isoamyl nitrite gives the corresponding nitrosyl alkoxide, (OEP)Os(NO)(O-i-C(5)H(11)). The related reactions of (OEP)Os(CO) or [(OEP)Os](2) with isoamyl thionitrite gives the (OEP)Os(NO)(S-i-C(5)H(11))

  （OEP）Os（CO）与亚硝酸正丁酯反应后，得到（OEP）Os（NO）（On-Bu）反式加成产物（OEP =八乙基卟啉二阴离子）。同样，（OEP）Os（CO）或[（OEP）Os]（2）与亚硝酸异戊酯的反应得到相应的亚硝酰基醇盐，（OEP）Os（NO）（OiC（5）H（11））。（OEP）Os（CO）或[（OEP）Os]（2）与异戊基亚硝酸亚硫酯的相关反应给出了（OEP）Os（NO）（SiC（5）H（11））亚硫基硫醇盐。[（OEP）Os]（2）（PF（6））（2）试剂与异戊基亚硝酸硫的反应生成亚硝基化产物[（OEP）Os（NO）] PF（6），将其阴离子水解为给出可分离的二氟磷酸盐（OEP）Os（NO）（O（2）PF（2））衍生物。有趣的是，O（2）NC（6）H（4）N = NSPh与[（OEP）Os]（2）的反应产生了（OEP）Os（SPh）（2）产物，但失去了芳基偶氮片段。（OEP）Os（NO）（On-Bu）的固态结构，