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Isotope effects in (195)Pt NMR spectroscopy: unique (35/37)Cl- and (16/18)O-resolved "fingerprints" for all [PtCl6-n(OH)n](2-) (n = 1-5) anions in an alkaline solution and the implications of the trans influence
A detailed analysis of the intrinsic (1)Δ(195)Pt((37/35)Cl) and (1)Δ(195)Pt((18/16)O) isotope 128.8 MHz (195)Pt NMR profiles of the series of kinetically inert [PtCl6-n(OH)n](2-) (n = 1-5) anions generated in strongly alkaline aqueous solutions shows that each (195)Pt NMR resonance of the [Pt(35/37)...
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Published in: | Inorganic chemistry 2015-03, Vol.54 (6), p.2752-2764 |
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creator | Engelbrecht, Leon Murray, Pieter Koch, Klaus R |
description | A detailed analysis of the intrinsic (1)Δ(195)Pt((37/35)Cl) and (1)Δ(195)Pt((18/16)O) isotope 128.8 MHz (195)Pt NMR profiles of the series of kinetically inert [PtCl6-n(OH)n](2-) (n = 1-5) anions generated in strongly alkaline aqueous solutions shows that each (195)Pt NMR resonance of the [Pt(35/37)Cl6-n((16/18)OH)n](2-) (n = 1-5) anions is resolved only into [(6 - n) + 1 for n = 1-5] (35/37)Cl isotopologues at 293 K. Evidently, the greater trans influence of the hydroxido ligand in the order OH(-) > Cl(-) > H2O in [PtCl6-n(OH)n](2-) (n = 1-5) complexes results in somewhat longer Pt-Cl bond displacements trans to the hydroxido ligands, resulting in the absence of isotopomer effects in the [PtCl6-n(OH)n](2-) (n = 1-5) anions in contrast to that observed in the corresponding [PtCl6-n(H2O)n]((2-n)-) (n = 1-5) complexes. In suitably (18)O-enriched sodium hydroxide solutions, additional intrinsic (1)Δ(195)Pt((18/16)O) isotope effects are remarkably well-resolved into unique isotopologue- and isotopomer-based (195)Pt NMR profiles, ascribable to the higher trans influence of the OH(-) ligand. The consequent significantly shorter Pt-OH bonds in these anions emphasize (16/18)O isotopomer effects in the (195)Pt NMR peaks of [Pt(35/37)Cl6-n((16/18)OH)n](2-) (n = 1-5) for magnetically nonequivalent (16/18)OH isotopomers statistically possible in some isotopologues. These (195)Pt NMR profiles constitute unique NMR "fingerprints", useful for the unambiguous assignment of the series of [PtCl6-n(OH)n](2-) anions including their possible cis/trans/fac/mer stereoisomers in such solutions, without a need for accurate chemical shift measurements. |
doi_str_mv | 10.1021/ic502901d |
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Evidently, the greater trans influence of the hydroxido ligand in the order OH(-) > Cl(-) > H2O in [PtCl6-n(OH)n](2-) (n = 1-5) complexes results in somewhat longer Pt-Cl bond displacements trans to the hydroxido ligands, resulting in the absence of isotopomer effects in the [PtCl6-n(OH)n](2-) (n = 1-5) anions in contrast to that observed in the corresponding [PtCl6-n(H2O)n]((2-n)-) (n = 1-5) complexes. In suitably (18)O-enriched sodium hydroxide solutions, additional intrinsic (1)Δ(195)Pt((18/16)O) isotope effects are remarkably well-resolved into unique isotopologue- and isotopomer-based (195)Pt NMR profiles, ascribable to the higher trans influence of the OH(-) ligand. The consequent significantly shorter Pt-OH bonds in these anions emphasize (16/18)O isotopomer effects in the (195)Pt NMR peaks of [Pt(35/37)Cl6-n((16/18)OH)n](2-) (n = 1-5) for magnetically nonequivalent (16/18)OH isotopomers statistically possible in some isotopologues. These (195)Pt NMR profiles constitute unique NMR "fingerprints", useful for the unambiguous assignment of the series of [PtCl6-n(OH)n](2-) anions including their possible cis/trans/fac/mer stereoisomers in such solutions, without a need for accurate chemical shift measurements.</description><identifier>EISSN: 1520-510X</identifier><identifier>DOI: 10.1021/ic502901d</identifier><identifier>PMID: 25699480</identifier><language>eng</language><publisher>United States</publisher><ispartof>Inorganic chemistry, 2015-03, Vol.54 (6), p.2752-2764</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/25699480$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Engelbrecht, Leon</creatorcontrib><creatorcontrib>Murray, Pieter</creatorcontrib><creatorcontrib>Koch, Klaus R</creatorcontrib><title>Isotope effects in (195)Pt NMR spectroscopy: unique (35/37)Cl- and (16/18)O-resolved "fingerprints" for all [PtCl6-n(OH)n](2-) (n = 1-5) anions in an alkaline solution and the implications of the trans influence</title><title>Inorganic chemistry</title><addtitle>Inorg Chem</addtitle><description>A detailed analysis of the intrinsic (1)Δ(195)Pt((37/35)Cl) and (1)Δ(195)Pt((18/16)O) isotope 128.8 MHz (195)Pt NMR profiles of the series of kinetically inert [PtCl6-n(OH)n](2-) (n = 1-5) anions generated in strongly alkaline aqueous solutions shows that each (195)Pt NMR resonance of the [Pt(35/37)Cl6-n((16/18)OH)n](2-) (n = 1-5) anions is resolved only into [(6 - n) + 1 for n = 1-5] (35/37)Cl isotopologues at 293 K. Evidently, the greater trans influence of the hydroxido ligand in the order OH(-) > Cl(-) > H2O in [PtCl6-n(OH)n](2-) (n = 1-5) complexes results in somewhat longer Pt-Cl bond displacements trans to the hydroxido ligands, resulting in the absence of isotopomer effects in the [PtCl6-n(OH)n](2-) (n = 1-5) anions in contrast to that observed in the corresponding [PtCl6-n(H2O)n]((2-n)-) (n = 1-5) complexes. In suitably (18)O-enriched sodium hydroxide solutions, additional intrinsic (1)Δ(195)Pt((18/16)O) isotope effects are remarkably well-resolved into unique isotopologue- and isotopomer-based (195)Pt NMR profiles, ascribable to the higher trans influence of the OH(-) ligand. The consequent significantly shorter Pt-OH bonds in these anions emphasize (16/18)O isotopomer effects in the (195)Pt NMR peaks of [Pt(35/37)Cl6-n((16/18)OH)n](2-) (n = 1-5) for magnetically nonequivalent (16/18)OH isotopomers statistically possible in some isotopologues. These (195)Pt NMR profiles constitute unique NMR "fingerprints", useful for the unambiguous assignment of the series of [PtCl6-n(OH)n](2-) anions including their possible cis/trans/fac/mer stereoisomers in such solutions, without a need for accurate chemical shift measurements.</description><issn>1520-510X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><recordid>eNo1kd9qFTEQxoMgtra98AUk9Gr3Ij35s8nJCl6Ug9pC7SmiIIgccrITjeYk6yYr9Dl9oYZthYGBmd98H3yD0CtGLxjlbOWtpLynbHiGjpnklEhGvx6hlzn_opT2olMv0BGXqu87TY_Rv-ucShoBg3NgS8Y-4ob1sr0r-PbjJ5zHOp1Stmm8f4Pn6P_MgBshV2LdbgLBJg6VVyum2y2ZIKfwFwZ87nz8AdM4-VjyOXZpwiYE_O2ubIIisdletfF7w0mLm4jfYkZkW5V8iou_qRV-m-Aj4Co4l7pYjMpPwP4wBm9NWeDkllmZzHLpwgzRwil67kzIcPbUT9CX9-8-b67IzfbD9ebyhoyMq0L2kgkw4PaUKdCaOasZFVzvdSfAcsGlo3Q9SC1tN2hr-l72nbCKcaPEWlpxgppH3XFKNZZcdgefLYRgIqQ575hSHacdZ7qir5_QeX-AYVeTOZjpfvf_EeIBTQ6EGg</recordid><startdate>20150316</startdate><enddate>20150316</enddate><creator>Engelbrecht, Leon</creator><creator>Murray, Pieter</creator><creator>Koch, Klaus R</creator><scope>NPM</scope><scope>7X8</scope></search><sort><creationdate>20150316</creationdate><title>Isotope effects in (195)Pt NMR spectroscopy: unique (35/37)Cl- and (16/18)O-resolved "fingerprints" for all [PtCl6-n(OH)n](2-) (n = 1-5) anions in an alkaline solution and the implications of the trans influence</title><author>Engelbrecht, Leon ; Murray, Pieter ; Koch, Klaus R</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-p126t-b513eaefb016e881fc810328b843ec2325f007d585c4d8ca995943c612a6375c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Engelbrecht, Leon</creatorcontrib><creatorcontrib>Murray, Pieter</creatorcontrib><creatorcontrib>Koch, Klaus R</creatorcontrib><collection>PubMed</collection><collection>MEDLINE - Academic</collection><jtitle>Inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Engelbrecht, Leon</au><au>Murray, Pieter</au><au>Koch, Klaus R</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Isotope effects in (195)Pt NMR spectroscopy: unique (35/37)Cl- and (16/18)O-resolved "fingerprints" for all [PtCl6-n(OH)n](2-) (n = 1-5) anions in an alkaline solution and the implications of the trans influence</atitle><jtitle>Inorganic chemistry</jtitle><addtitle>Inorg Chem</addtitle><date>2015-03-16</date><risdate>2015</risdate><volume>54</volume><issue>6</issue><spage>2752</spage><epage>2764</epage><pages>2752-2764</pages><eissn>1520-510X</eissn><abstract>A detailed analysis of the intrinsic (1)Δ(195)Pt((37/35)Cl) and (1)Δ(195)Pt((18/16)O) isotope 128.8 MHz (195)Pt NMR profiles of the series of kinetically inert [PtCl6-n(OH)n](2-) (n = 1-5) anions generated in strongly alkaline aqueous solutions shows that each (195)Pt NMR resonance of the [Pt(35/37)Cl6-n((16/18)OH)n](2-) (n = 1-5) anions is resolved only into [(6 - n) + 1 for n = 1-5] (35/37)Cl isotopologues at 293 K. Evidently, the greater trans influence of the hydroxido ligand in the order OH(-) > Cl(-) > H2O in [PtCl6-n(OH)n](2-) (n = 1-5) complexes results in somewhat longer Pt-Cl bond displacements trans to the hydroxido ligands, resulting in the absence of isotopomer effects in the [PtCl6-n(OH)n](2-) (n = 1-5) anions in contrast to that observed in the corresponding [PtCl6-n(H2O)n]((2-n)-) (n = 1-5) complexes. In suitably (18)O-enriched sodium hydroxide solutions, additional intrinsic (1)Δ(195)Pt((18/16)O) isotope effects are remarkably well-resolved into unique isotopologue- and isotopomer-based (195)Pt NMR profiles, ascribable to the higher trans influence of the OH(-) ligand. The consequent significantly shorter Pt-OH bonds in these anions emphasize (16/18)O isotopomer effects in the (195)Pt NMR peaks of [Pt(35/37)Cl6-n((16/18)OH)n](2-) (n = 1-5) for magnetically nonequivalent (16/18)OH isotopomers statistically possible in some isotopologues. These (195)Pt NMR profiles constitute unique NMR "fingerprints", useful for the unambiguous assignment of the series of [PtCl6-n(OH)n](2-) anions including their possible cis/trans/fac/mer stereoisomers in such solutions, without a need for accurate chemical shift measurements.</abstract><cop>United States</cop><pmid>25699480</pmid><doi>10.1021/ic502901d</doi><tpages>13</tpages></addata></record> |
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title | Isotope effects in (195)Pt NMR spectroscopy: unique (35/37)Cl- and (16/18)O-resolved "fingerprints" for all [PtCl6-n(OH)n](2-) (n = 1-5) anions in an alkaline solution and the implications of the trans influence |
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