Energetics of halogen bonding of group 10 metal fluoride complexes.
A study is presented of the thermodynamics of the halogen-bonding interaction of C(6)F(5)I with a series of structurally similar group 10 metal fluoride complexes trans-[Ni(F)(2-C(5)NF(4))(PCy(3))(2)] (2), trans-[Pd(F)(4-C(5)NF(4))(PCy(3))(2)] (3), trans-[Pt(F){2-C(5)NF(2)H(CF(3))}(PR(3))(2)] (4a, R...
| Main Authors: | , , , , , |
|---|---|
| Format: | Journal article |
| Language: | English |
| Published: |
2011
|
| _version_ | 1826273712068886528 |
|---|---|
| author | Beweries, T Brammer, L Jasim, N McGrady, J Perutz, R Whitwood, A |
| author_facet | Beweries, T Brammer, L Jasim, N McGrady, J Perutz, R Whitwood, A |
| author_sort | Beweries, T |
| collection | OXFORD |
| description | A study is presented of the thermodynamics of the halogen-bonding interaction of C(6)F(5)I with a series of structurally similar group 10 metal fluoride complexes trans-[Ni(F)(2-C(5)NF(4))(PCy(3))(2)] (2), trans-[Pd(F)(4-C(5)NF(4))(PCy(3))(2)] (3), trans-[Pt(F){2-C(5)NF(2)H(CF(3))}(PR(3))(2)] (4a, R = Cy; 4bR = iPr) and trans-[Ni(F){2-C(5)NF(2)H(CF(3))}(PCy(3))(2)] (5a) in toluene solution. (19)F NMR titration experiments are used to determine binding constants, enthalpies and entropies of these interactions (2.4 ≤ K(300) ≤ 5.2; -25 ≤ ΔH(o) ≤ -16 kJ mol(-1); -73 ≤ ΔS(o) ≤ -49 J K(-1) mol(-1)). The data for -ΔH(o) for the halogen bonding follow a trend Ni < Pd < Pt. The fluoropyridyl ligand is shown to have a negligible influence on the thermodynamic data, but the influence of the phosphine ligand is significant. We also show that the value of the spin-spin coupling constant J(PtF) increases substantially with adduct formation. X-ray crystallographic data for Ni complexes 5a and 5c are compared to previously published data for a platinum analogue. We show by experiment and computation that the difference between Pt-X and Ni-X (X = F, C, P) bond lengths is greatest for X = F, consistent with F(2pπ)-Pt(5dπ) repulsive interactions. DFT calculations on the metal fluoride complexes show the very negative electrostatic potential around the fluoride. Calculations of the enthalpy of adduct formation show energies of -18.8 and -22.8 kJ mol(-1) for Ni and Pt complexes of types 5 and 4, respectively, in excellent agreement with experiment. |
| first_indexed | 2024-03-06T22:32:23Z |
| format | Journal article |
| id | oxford-uuid:58b3d298-309d-4756-8999-2982738b38e7 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T22:32:23Z |
| publishDate | 2011 |
| record_format | dspace |
| spelling | oxford-uuid:58b3d298-309d-4756-8999-2982738b38e72022-03-26T17:05:13ZEnergetics of halogen bonding of group 10 metal fluoride complexes.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:58b3d298-309d-4756-8999-2982738b38e7EnglishSymplectic Elements at Oxford2011Beweries, TBrammer, LJasim, NMcGrady, JPerutz, RWhitwood, AA study is presented of the thermodynamics of the halogen-bonding interaction of C(6)F(5)I with a series of structurally similar group 10 metal fluoride complexes trans-[Ni(F)(2-C(5)NF(4))(PCy(3))(2)] (2), trans-[Pd(F)(4-C(5)NF(4))(PCy(3))(2)] (3), trans-[Pt(F){2-C(5)NF(2)H(CF(3))}(PR(3))(2)] (4a, R = Cy; 4bR = iPr) and trans-[Ni(F){2-C(5)NF(2)H(CF(3))}(PCy(3))(2)] (5a) in toluene solution. (19)F NMR titration experiments are used to determine binding constants, enthalpies and entropies of these interactions (2.4 ≤ K(300) ≤ 5.2; -25 ≤ ΔH(o) ≤ -16 kJ mol(-1); -73 ≤ ΔS(o) ≤ -49 J K(-1) mol(-1)). The data for -ΔH(o) for the halogen bonding follow a trend Ni < Pd < Pt. The fluoropyridyl ligand is shown to have a negligible influence on the thermodynamic data, but the influence of the phosphine ligand is significant. We also show that the value of the spin-spin coupling constant J(PtF) increases substantially with adduct formation. X-ray crystallographic data for Ni complexes 5a and 5c are compared to previously published data for a platinum analogue. We show by experiment and computation that the difference between Pt-X and Ni-X (X = F, C, P) bond lengths is greatest for X = F, consistent with F(2pπ)-Pt(5dπ) repulsive interactions. DFT calculations on the metal fluoride complexes show the very negative electrostatic potential around the fluoride. Calculations of the enthalpy of adduct formation show energies of -18.8 and -22.8 kJ mol(-1) for Ni and Pt complexes of types 5 and 4, respectively, in excellent agreement with experiment. |
| spellingShingle | Beweries, T Brammer, L Jasim, N McGrady, J Perutz, R Whitwood, A Energetics of halogen bonding of group 10 metal fluoride complexes. |
| title | Energetics of halogen bonding of group 10 metal fluoride complexes. |
| title_full | Energetics of halogen bonding of group 10 metal fluoride complexes. |
| title_fullStr | Energetics of halogen bonding of group 10 metal fluoride complexes. |
| title_full_unstemmed | Energetics of halogen bonding of group 10 metal fluoride complexes. |
| title_short | Energetics of halogen bonding of group 10 metal fluoride complexes. |
| title_sort | energetics of halogen bonding of group 10 metal fluoride complexes |
| work_keys_str_mv | AT beweriest energeticsofhalogenbondingofgroup10metalfluoridecomplexes AT brammerl energeticsofhalogenbondingofgroup10metalfluoridecomplexes AT jasimn energeticsofhalogenbondingofgroup10metalfluoridecomplexes AT mcgradyj energeticsofhalogenbondingofgroup10metalfluoridecomplexes AT perutzr energeticsofhalogenbondingofgroup10metalfluoridecomplexes AT whitwooda energeticsofhalogenbondingofgroup10metalfluoridecomplexes |