Copper Clusters Containing Hydrides in Trigonal Pyramidal Geometry
Structurally precise copper hydrides [Cu11H2{S2P(O i Pr)2}6(CCR)3], R = Ph (1), C6H4F (2), and C6H4OMe (3), were first synthesized from the polyhydrido copper cluster [Cu20H11{S2P(O i Pr)2}9] with nine equivalents of terminal alkynes. Later, their isolated yields were significantly improved by di...
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| Veröffentlicht in: | Inorganic chemistry 2020-02, Vol.59 (4), p.2536-2547 |
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| creator | Brocha Silalahi, Rhone P Huang, Guan-Rong Liao, Jian-Hong Chiu, Tzu-Hao Chakrahari, Kiran Kumarvarma Wang, Xiaoping Cartron, Julien Kahlal, Samia Saillard, Jean-Yves Liu, C. W |
| description | Structurally precise copper hydrides [Cu11H2{S2P(O i Pr)2}6(CCR)3], R = Ph (1), C6H4F (2), and C6H4OMe (3), were first synthesized from the polyhydrido copper cluster [Cu20H11{S2P(O i Pr)2}9] with nine equivalents of terminal alkynes. Later, their isolated yields were significantly improved by direct synthesis from [Cu(CH3CN)4](PF6), [NH4][S2P(O i Pr)2], NaBH4, and alkynes along with NEt3 in THF. 1, 2, and 3 were fully characterized by single-crystal X-ray diffraction, ESI-MS, and multinuclear NMR spectroscopy. All three clustershave 11 copper atoms, adopting 3,3,4,4,4-pentacapped trigonal prismatic geometry, with two hydrides inside the Cu11 cage, the position of which was ascertained by a single-crystal neutron diffraction structure of cluster 1 co-crystallized with a [Cu7(H){S2P(O i Pr)2}6] (4) cluster. Six dithiophosphate and three alkynyl ligands stabilize the Cu11H2 core in which the two hydrides adopt a trigonal pyramidal coordination mode. This coordination mode is so far unprecedented for hydride. The 1H NMR resonance frequency of the two hydrides appears at 4.8 ppm, a value further confirmed by 2H NMR spectroscopy for their deuteride derivatives [Cu11(D)2{S2P(O i Pr)2}6(CCR)3]. A DFT investigation allows understanding the bonding within this new type of copper(I) hydrides. |
| doi_str_mv | 10.1021/acs.inorgchem.9b03501 |
| format | Article |
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W</creator><creatorcontrib>Brocha Silalahi, Rhone P ; Huang, Guan-Rong ; Liao, Jian-Hong ; Chiu, Tzu-Hao ; Chakrahari, Kiran Kumarvarma ; Wang, Xiaoping ; Cartron, Julien ; Kahlal, Samia ; Saillard, Jean-Yves ; Liu, C. W ; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)</creatorcontrib><description>Structurally precise copper hydrides [Cu11H2{S2P(O i Pr)2}6(CCR)3], R = Ph (1), C6H4F (2), and C6H4OMe (3), were first synthesized from the polyhydrido copper cluster [Cu20H11{S2P(O i Pr)2}9] with nine equivalents of terminal alkynes. Later, their isolated yields were significantly improved by direct synthesis from [Cu(CH3CN)4](PF6), [NH4][S2P(O i Pr)2], NaBH4, and alkynes along with NEt3 in THF. 1, 2, and 3 were fully characterized by single-crystal X-ray diffraction, ESI-MS, and multinuclear NMR spectroscopy. All three clustershave 11 copper atoms, adopting 3,3,4,4,4-pentacapped trigonal prismatic geometry, with two hydrides inside the Cu11 cage, the position of which was ascertained by a single-crystal neutron diffraction structure of cluster 1 co-crystallized with a [Cu7(H){S2P(O i Pr)2}6] (4) cluster. Six dithiophosphate and three alkynyl ligands stabilize the Cu11H2 core in which the two hydrides adopt a trigonal pyramidal coordination mode. This coordination mode is so far unprecedented for hydride. The 1H NMR resonance frequency of the two hydrides appears at 4.8 ppm, a value further confirmed by 2H NMR spectroscopy for their deuteride derivatives [Cu11(D)2{S2P(O i Pr)2}6(CCR)3]. A DFT investigation allows understanding the bonding within this new type of copper(I) hydrides.</description><identifier>ISSN: 0020-1669</identifier><identifier>EISSN: 1520-510X</identifier><identifier>DOI: 10.1021/acs.inorgchem.9b03501</identifier><identifier>PMID: 31977197</identifier><language>eng</language><publisher>WASHINGTON: American Chemical Society</publisher><subject>Anions ; Chemical Sciences ; Chemistry ; Chemistry, Inorganic & Nuclear ; Copper ; Hydrocarbons ; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY ; Ligands ; Metal clusters ; Physical Sciences ; Science & Technology</subject><ispartof>Inorganic chemistry, 2020-02, Vol.59 (4), p.2536-2547</ispartof><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>true</woscitedreferencessubscribed><woscitedreferencescount>36</woscitedreferencescount><woscitedreferencesoriginalsourcerecordid>wos000514488400044</woscitedreferencesoriginalsourcerecordid><citedby>FETCH-LOGICAL-a525t-9c47c8c855980f44e768ffc885cd30b8bc178ef7f677dae22f6acaa88c80b563</citedby><cites>FETCH-LOGICAL-a525t-9c47c8c855980f44e768ffc885cd30b8bc178ef7f677dae22f6acaa88c80b563</cites><orcidid>0000-0003-4469-7922 ; 0000-0001-6028-6889 ; 0000-0003-0801-6499 ; 0000-0001-7143-8112 ; 0000-0001-5719-553X ; 0000000344697922 ; 0000000308016499 ; 0000000171438112 ; 0000000160286889</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.9b03501$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.9b03501$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>230,315,782,786,887,2769,27085,27933,27934,28257,56747,56797</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/31977197$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://univ-rennes.hal.science/hal-02472166$$DView record in HAL$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/servlets/purl/1631228$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Brocha Silalahi, Rhone P</creatorcontrib><creatorcontrib>Huang, Guan-Rong</creatorcontrib><creatorcontrib>Liao, Jian-Hong</creatorcontrib><creatorcontrib>Chiu, Tzu-Hao</creatorcontrib><creatorcontrib>Chakrahari, Kiran Kumarvarma</creatorcontrib><creatorcontrib>Wang, Xiaoping</creatorcontrib><creatorcontrib>Cartron, Julien</creatorcontrib><creatorcontrib>Kahlal, Samia</creatorcontrib><creatorcontrib>Saillard, Jean-Yves</creatorcontrib><creatorcontrib>Liu, C. W</creatorcontrib><creatorcontrib>Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)</creatorcontrib><title>Copper Clusters Containing Hydrides in Trigonal Pyramidal Geometry</title><title>Inorganic chemistry</title><addtitle>INORG CHEM</addtitle><addtitle>Inorg. Chem</addtitle><description>Structurally precise copper hydrides [Cu11H2{S2P(O i Pr)2}6(CCR)3], R = Ph (1), C6H4F (2), and C6H4OMe (3), were first synthesized from the polyhydrido copper cluster [Cu20H11{S2P(O i Pr)2}9] with nine equivalents of terminal alkynes. Later, their isolated yields were significantly improved by direct synthesis from [Cu(CH3CN)4](PF6), [NH4][S2P(O i Pr)2], NaBH4, and alkynes along with NEt3 in THF. 1, 2, and 3 were fully characterized by single-crystal X-ray diffraction, ESI-MS, and multinuclear NMR spectroscopy. All three clustershave 11 copper atoms, adopting 3,3,4,4,4-pentacapped trigonal prismatic geometry, with two hydrides inside the Cu11 cage, the position of which was ascertained by a single-crystal neutron diffraction structure of cluster 1 co-crystallized with a [Cu7(H){S2P(O i Pr)2}6] (4) cluster. Six dithiophosphate and three alkynyl ligands stabilize the Cu11H2 core in which the two hydrides adopt a trigonal pyramidal coordination mode. This coordination mode is so far unprecedented for hydride. The 1H NMR resonance frequency of the two hydrides appears at 4.8 ppm, a value further confirmed by 2H NMR spectroscopy for their deuteride derivatives [Cu11(D)2{S2P(O i Pr)2}6(CCR)3]. A DFT investigation allows understanding the bonding within this new type of copper(I) hydrides.</description><subject>Anions</subject><subject>Chemical Sciences</subject><subject>Chemistry</subject><subject>Chemistry, Inorganic & Nuclear</subject><subject>Copper</subject><subject>Hydrocarbons</subject><subject>INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY</subject><subject>Ligands</subject><subject>Metal clusters</subject><subject>Physical Sciences</subject><subject>Science & Technology</subject><issn>0020-1669</issn><issn>1520-510X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><sourceid>AOWDO</sourceid><recordid>eNqNkUGP2yAQhVHVVTfd9ie0snrqqkoKGAw-bq3tZqVI20MOvSGMxwkrG1LArfLvS-Q01-4B8YS-NzPMQ-gDwSuCKfmqTVxZ58PO7GFc1S0uOSav0IJwipec4J-v0QLjrElV1dfobYzPGOO6ZNUbdF2SWoh8Fuhb4w8HCEUzTDFBiEXjXdLWWbcr1scu2A5iYV2xDXbnnR6KH8egR9tl9QB-hBSO79BVr4cI78_3Ddp-v9826-Xm6eGxudssNac8LWvDhJFGcl5L3DMGopJ9b6TkpitxK1tDhIRe9JUQnQZK-0obrWW24JZX5Q36NJf1MVkVjU1g9sY7ByYpUpWEUpmh2xna60Edgh11OCqvrVrfbdTpDVMmaF7Jb5LZzzN7CP7XBDGp0UYDw6Ad-CkqWjLOMSelyCifURN8jAH6S22C1SkOleNQlzjUOY7s-3huMbUjdBfXv_1n4MsM_IHW9_lT4AxcsBwYJ4xJybJiLNPy5XRjk07Wu8ZPLmUrma2nQZ_9FHKW8T_T_wWDrLpm</recordid><startdate>20200217</startdate><enddate>20200217</enddate><creator>Brocha Silalahi, Rhone P</creator><creator>Huang, Guan-Rong</creator><creator>Liao, Jian-Hong</creator><creator>Chiu, Tzu-Hao</creator><creator>Chakrahari, Kiran Kumarvarma</creator><creator>Wang, Xiaoping</creator><creator>Cartron, Julien</creator><creator>Kahlal, Samia</creator><creator>Saillard, Jean-Yves</creator><creator>Liu, C. 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(ORNL), Oak Ridge, TN (United States)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Copper Clusters Containing Hydrides in Trigonal Pyramidal Geometry</atitle><jtitle>Inorganic chemistry</jtitle><stitle>INORG CHEM</stitle><addtitle>Inorg. Chem</addtitle><date>2020-02-17</date><risdate>2020</risdate><volume>59</volume><issue>4</issue><spage>2536</spage><epage>2547</epage><pages>2536-2547</pages><issn>0020-1669</issn><eissn>1520-510X</eissn><abstract>Structurally precise copper hydrides [Cu11H2{S2P(O i Pr)2}6(CCR)3], R = Ph (1), C6H4F (2), and C6H4OMe (3), were first synthesized from the polyhydrido copper cluster [Cu20H11{S2P(O i Pr)2}9] with nine equivalents of terminal alkynes. Later, their isolated yields were significantly improved by direct synthesis from [Cu(CH3CN)4](PF6), [NH4][S2P(O i Pr)2], NaBH4, and alkynes along with NEt3 in THF. 1, 2, and 3 were fully characterized by single-crystal X-ray diffraction, ESI-MS, and multinuclear NMR spectroscopy. All three clustershave 11 copper atoms, adopting 3,3,4,4,4-pentacapped trigonal prismatic geometry, with two hydrides inside the Cu11 cage, the position of which was ascertained by a single-crystal neutron diffraction structure of cluster 1 co-crystallized with a [Cu7(H){S2P(O i Pr)2}6] (4) cluster. Six dithiophosphate and three alkynyl ligands stabilize the Cu11H2 core in which the two hydrides adopt a trigonal pyramidal coordination mode. This coordination mode is so far unprecedented for hydride. The 1H NMR resonance frequency of the two hydrides appears at 4.8 ppm, a value further confirmed by 2H NMR spectroscopy for their deuteride derivatives [Cu11(D)2{S2P(O i Pr)2}6(CCR)3]. 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| subjects | Anions Chemical Sciences Chemistry Chemistry, Inorganic & Nuclear Copper Hydrocarbons INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY Ligands Metal clusters Physical Sciences Science & Technology |
| title | Copper Clusters Containing Hydrides in Trigonal Pyramidal Geometry |
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