Stephanie M. Ingwer, Christopher J. Yoler, Todd Reynolds, Daniel R. Griffith, Chip Nataro
{"title":"[Fe(CO)3(η - 4-6-外氧-(PPh2R)环庚-2,4-二烯-1- 1][BF4] （R = Me或tBu）的x射线结构","authors":"Stephanie M. Ingwer, Christopher J. Yoler, Todd Reynolds, Daniel R. Griffith, Chip Nataro","doi":"10.1007/s10870-024-01031-4","DOIUrl":null,"url":null,"abstract":"<div><p>The structures of [Fe(CO)<sub>3</sub>(η<sup>4</sup>-6-<i>exo</i>-(methyldiphenylphosphine)cyclohepta-2,4-dien-1-one][BF<sub>4</sub>] [orthorhombic, <i>a</i> = 12.3269(4), <i>b</i><b> = </b>13.5243(5), <i>c</i> = 13.7127(4), space group Pna2<sub>1</sub>] and [Fe(CO)<sub>3</sub>(η<sup>4</sup>-6-<i>exo</i>-(<i>tert</i>-butyldiphenylphosphine)cyclohepta-2,4-dien-1-one][BF<sub>4</sub>] [monoclinic, <i>a</i> = 9.7947(3), <i>b</i><b> = </b>12.8766(3), <i>c</i> = 20.2168(5), <i>β</i> = 91.089(3), space group P2<sub>1</sub>/c] have been determined. The disordered tetrafluoroborate ion in [Fe(CO)<sub>3</sub>(η<sup>4</sup>-6-<i>exo</i>-(methyldiphenylphosphine)cyclohepta-2,4-dien-1-one][BF<sub>4</sub>] sits between two of the cations and displays interactions with hydrogen atoms in the <i>ortho</i>- position of the phenyl rings, the methyl group and the 6-position of the seven-membered ring. There is also close contact between the ketone oxygen atom and two protons in another cation, a proton of the methyl group and the proton in the 5-position of the seven-membered ring. The tetrafluoroborate anion in [Fe(CO)<sub>3</sub>(η<sup>4</sup>-6-<i>exo</i>-(<i>tert</i>-butyldiphenylphosphine)cyclohepta-2,4-dien-1-one][BF<sub>4</sub>] is not disordered and shows close contacts with protons in three cation units. In one cation the interaction is with two protons from separate methyl groups of the <i>tert</i>-butyl substituent. The remaining interactions are with a proton in the <i>ortho</i>- position of a phenyl ring in one cation and the proton in the 2-position of the seven-membered ring. There is also an interaction between the ketone oxygen and a proton from the <i>tert</i>-butyl group in another cationic unit.</p><h3>Graphical abstract</h3><p>Addition of PPh<sub>2</sub>R (R = Me or <sup><i>t</i></sup>Bu) to [Fe(CO)<sub>3</sub>(η<sup>5</sup>-cyclohepta-2,4-dien-5-yl-1-one)][BF<sub>4</sub>] results in <i>exo</i>- attack at the coordinated ring forming the [Fe(CO)<sub>3</sub>(η<sup>4</sup>-6-<i>exo</i>-(PPh<sub>2</sub>R)cyclohepta-2,4-dien-1-one][BF<sub>4</sub>] compounds, both of which were structurally characterized.</p>\n<div><figure><div><div><picture><img></picture></div></div></figure></div></div>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"55 1","pages":"35 - 40"},"PeriodicalIF":0.4000,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"The X-ray Structures of [Fe(CO)3(η4-6-exo-(PPh2R)cyclohepta-2,4-dien-1-one][BF4] (R = Me or tBu)\",\"authors\":\"Stephanie M. Ingwer, Christopher J. Yoler, Todd Reynolds, Daniel R. Griffith, Chip Nataro\",\"doi\":\"10.1007/s10870-024-01031-4\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The structures of [Fe(CO)<sub>3</sub>(η<sup>4</sup>-6-<i>exo</i>-(methyldiphenylphosphine)cyclohepta-2,4-dien-1-one][BF<sub>4</sub>] [orthorhombic, <i>a</i> = 12.3269(4), <i>b</i><b> = </b>13.5243(5), <i>c</i> = 13.7127(4), space group Pna2<sub>1</sub>] and [Fe(CO)<sub>3</sub>(η<sup>4</sup>-6-<i>exo</i>-(<i>tert</i>-butyldiphenylphosphine)cyclohepta-2,4-dien-1-one][BF<sub>4</sub>] [monoclinic, <i>a</i> = 9.7947(3), <i>b</i><b> = </b>12.8766(3), <i>c</i> = 20.2168(5), <i>β</i> = 91.089(3), space group P2<sub>1</sub>/c] have been determined. The disordered tetrafluoroborate ion in [Fe(CO)<sub>3</sub>(η<sup>4</sup>-6-<i>exo</i>-(methyldiphenylphosphine)cyclohepta-2,4-dien-1-one][BF<sub>4</sub>] sits between two of the cations and displays interactions with hydrogen atoms in the <i>ortho</i>- position of the phenyl rings, the methyl group and the 6-position of the seven-membered ring. There is also close contact between the ketone oxygen atom and two protons in another cation, a proton of the methyl group and the proton in the 5-position of the seven-membered ring. The tetrafluoroborate anion in [Fe(CO)<sub>3</sub>(η<sup>4</sup>-6-<i>exo</i>-(<i>tert</i>-butyldiphenylphosphine)cyclohepta-2,4-dien-1-one][BF<sub>4</sub>] is not disordered and shows close contacts with protons in three cation units. In one cation the interaction is with two protons from separate methyl groups of the <i>tert</i>-butyl substituent. The remaining interactions are with a proton in the <i>ortho</i>- position of a phenyl ring in one cation and the proton in the 2-position of the seven-membered ring. There is also an interaction between the ketone oxygen and a proton from the <i>tert</i>-butyl group in another cationic unit.</p><h3>Graphical abstract</h3><p>Addition of PPh<sub>2</sub>R (R = Me or <sup><i>t</i></sup>Bu) to [Fe(CO)<sub>3</sub>(η<sup>5</sup>-cyclohepta-2,4-dien-5-yl-1-one)][BF<sub>4</sub>] results in <i>exo</i>- attack at the coordinated ring forming the [Fe(CO)<sub>3</sub>(η<sup>4</sup>-6-<i>exo</i>-(PPh<sub>2</sub>R)cyclohepta-2,4-dien-1-one][BF<sub>4</sub>] compounds, both of which were structurally characterized.</p>\\n<div><figure><div><div><picture><img></picture></div></div></figure></div></div>\",\"PeriodicalId\":615,\"journal\":{\"name\":\"Journal of Chemical Crystallography\",\"volume\":\"55 1\",\"pages\":\"35 - 40\"},\"PeriodicalIF\":0.4000,\"publicationDate\":\"2024-10-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Chemical Crystallography\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s10870-024-01031-4\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CRYSTALLOGRAPHY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical Crystallography","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s10870-024-01031-4","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CRYSTALLOGRAPHY","Score":null,"Total":0}
引用次数: 0
摘要
确定了[Fe(CO)3(η - 4-6-外显-（甲基二苯基膦）环庚-2,4-二烯-1-one][BF4][正交，a = 12.3269(4), b = 13.5243(5), c = 13.7127(4)，空间群Pna21]和[Fe(CO)3(η - 4-6-外显-（叔丁基二苯基膦）环庚-2,4-二烯-1-one][BF4][单斜，a = 9.7947(3), b = 12.8766(3), c = 20.2168(5), β = 91.089(3)，空间群P21/c]的结构。[Fe(CO)3(η - 4-6-外显-（甲基二苯基膦）环庚-2,4-二烯-1- 1][BF4]中的无序四氟硼酸盐离子位于两个阳离子之间，并与苯基环的邻位氢原子、甲基和七元环的6位氢原子发生相互作用。酮氧原子与另一个阳离子上的两个质子、甲基的一个质子和七元环上5位的一个质子之间也有密切的接触。[Fe(CO)3(η - 4-6-外氧-（叔丁基二苯基膦）环庚-2,4-二烯-1- 1][BF4]中的四氟硼酸阴离子不无序，与三个阳离子单元中的质子密切接触。在一个阳离子中，它与来自叔丁基取代基不同甲基的两个质子相互作用。其余的相互作用是一个阳离子中苯基环邻位的质子和七元环中2位的质子。酮氧和另一个阳离子单元中叔丁基的质子之间也有相互作用。在[Fe(CO)3(η4-6-环庚-(PPh2R) -2,4-二烯-5-基-1- 1)][BF4]中加入PPh2R (R = Me或tBu)，在配位环上发生外键攻击，形成[Fe(CO)3(η4-6-外-(PPh2R)环庚-2,4-二烯-1- 1][BF4]化合物，两种化合物均具有结构表征。
The X-ray Structures of [Fe(CO)3(η4-6-exo-(PPh2R)cyclohepta-2,4-dien-1-one][BF4] (R = Me or tBu)
The structures of [Fe(CO)3(η4-6-exo-(methyldiphenylphosphine)cyclohepta-2,4-dien-1-one][BF4] [orthorhombic, a = 12.3269(4), b = 13.5243(5), c = 13.7127(4), space group Pna21] and [Fe(CO)3(η4-6-exo-(tert-butyldiphenylphosphine)cyclohepta-2,4-dien-1-one][BF4] [monoclinic, a = 9.7947(3), b = 12.8766(3), c = 20.2168(5), β = 91.089(3), space group P21/c] have been determined. The disordered tetrafluoroborate ion in [Fe(CO)3(η4-6-exo-(methyldiphenylphosphine)cyclohepta-2,4-dien-1-one][BF4] sits between two of the cations and displays interactions with hydrogen atoms in the ortho- position of the phenyl rings, the methyl group and the 6-position of the seven-membered ring. There is also close contact between the ketone oxygen atom and two protons in another cation, a proton of the methyl group and the proton in the 5-position of the seven-membered ring. The tetrafluoroborate anion in [Fe(CO)3(η4-6-exo-(tert-butyldiphenylphosphine)cyclohepta-2,4-dien-1-one][BF4] is not disordered and shows close contacts with protons in three cation units. In one cation the interaction is with two protons from separate methyl groups of the tert-butyl substituent. The remaining interactions are with a proton in the ortho- position of a phenyl ring in one cation and the proton in the 2-position of the seven-membered ring. There is also an interaction between the ketone oxygen and a proton from the tert-butyl group in another cationic unit.
Graphical abstract
Addition of PPh2R (R = Me or tBu) to [Fe(CO)3(η5-cyclohepta-2,4-dien-5-yl-1-one)][BF4] results in exo- attack at the coordinated ring forming the [Fe(CO)3(η4-6-exo-(PPh2R)cyclohepta-2,4-dien-1-one][BF4] compounds, both of which were structurally characterized.
期刊介绍：
Journal of Chemical Crystallography is an international and interdisciplinary publication dedicated to the rapid dissemination of research results in the general areas of crystallography and spectroscopy. Timely research reports detail topics in crystal chemistry and physics and their relation to problems of molecular structure; structural studies of solids, liquids, gases, and solutions involving spectroscopic, spectrometric, X-ray, and electron and neutron diffraction; and theoretical studies.
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