Cocrystallization of the dithiocarbamate complexes[M(S_(2)CNEt_(2))_(2)](M=Ni 1,Pd 2,Pt 3)and X-substituted perfluoroarenes(X=I,Br;1,2-dibromoperfluorobenzene FBrB and 1,2-diiodoperfluorobenzene FIB)gives isomorphous ...Cocrystallization of the dithiocarbamate complexes[M(S_(2)CNEt_(2))_(2)](M=Ni 1,Pd 2,Pt 3)and X-substituted perfluoroarenes(X=I,Br;1,2-dibromoperfluorobenzene FBrB and 1,2-diiodoperfluorobenzene FIB)gives isomorphous cocrystals of(1-3)·2(FBrB)and 1·2(FIB),correspondingly,whose structures were studied by single-crystal X-ray diffractometry.The crystal structures demonstrate similar intermolecular contact types:short arene MS_(4)…π-hole stacking contacts,X…S halogen bonds,C-H…X(X=Br,I)bonds and C-H…F hydrogen bonds.In these structures,the{d_(z^(2))-M^(Ⅱ)S_(4)}moiety functions as an integrated five-center acceptor(that includes a metal d_(z^(2))-orbital,even for a poorly d_(z^(2))-nucleophilic Ni^(Ⅱ) center)toward theπ-hole of an X-substituted perfluoroarene.This interaction provides stacking of inorganic and organic units furnishing the reverse sandwich structures.Density functional theory(DFT)calculations,in combination with quantum theory of atoms-in-molecules(QTAIM)and noncovalent interaction plot(NCIplot)analyses,supported the structure-defining role of the{MS_(4)}…π-hole contacts.The nucleophilicity of the{MS_(4)}cores toward electron deficient π-holes was verified from the molecular electrostatic potential surface(MEP)and electron density/electrostatic potential(ED/ESP)profiles,and atoms-in-molecules(AIM)charge analysis.The relatively strong{MS_(4)}…π-hole contact strength(interaction energies for an{MS_(4)}…π-hole 1:1 adduct range from^(-1)2.1 to^(-1)3.5 kcal mol^(-1))is probably due to the large overlap between the electron deficient π-cloud and the integrated{MS_(4)}nucleophilic core.The 1:1 adduct based on 3 demonstrates the largest strength(13.5 kcal mol^(-1))in the series and this strength agrees well with the higher d_(z^(2))-nucleophilicity of the Pt^(Ⅱ) center revealed by the MEP analysis(-33.6 kcal mol^(-1)).展开更多
Co-crystallization of dithiocarbamate complexes[M^(Ⅱ)(S_(2)CNEt_(2))_(2)](M=Cu 1,Ni 2,Pd 3,Pt 4)and 1,3,5-triiodotrifluorobenzene(FIB)gives an isomorphic series of(1-4)·2FIB co-crystals exhibiting quadruple Cu/N...Co-crystallization of dithiocarbamate complexes[M^(Ⅱ)(S_(2)CNEt_(2))_(2)](M=Cu 1,Ni 2,Pd 3,Pt 4)and 1,3,5-triiodotrifluorobenzene(FIB)gives an isomorphic series of(1-4)·2FIB co-crystals exhibiting quadruple Cu/Ni/Pd/Pt isostructural exchange.In the structures of(1-4)·2FIB,the halogen-bonded C-I…M(Ni,Pd,Pt)and semicoordination M…I-C(Cu)metal-involving contacts were identified by X-ray diffractometry and their nature was verified theoretically.The directionality of the I_(σ-hole)…d_(z)^(2)M^(Ⅱ) and M^(Ⅱ)…I_(electron belt)interactions depends on the identity of a metal center:on going from a rather electrophilic Cu^(Ⅱ) to substantially more nucleophilic Ni^(Ⅱ),Pd^(Ⅱ),and Pt^(Ⅱ) centers,we observed the electron belt-to-σ-hole switch of a noncovalently bound iodine(I)of FIB and,correspondingly,its shift from semicoordination to halogen bonding.The negative values of the electrostatic potentials(given in parentheses)were estimated for all metal centers and they decrease in the order Cu^(Ⅱ)(-8.8)>Ni^(Ⅱ)(-24.5)>Pd^(Ⅱ)(-28.6)>Pt^(Ⅱ)(-33.3 kcal mol^(-1)).Despite the negative potentials at all M^(Ⅱ)s,the semicoordinative contact Cu…I was established by the recognition of the LP(I)→LP*(Cu)charge transfer using natural bond orbital(NBO)analysis and the comparison of electron density(ED)and electrostatic potential(ESP)minima positions along the I…Cu bond paths.In the case of the rather nucleophilic(although positively charged)Pd^(Ⅱ) and Pt^(Ⅱ) centers,the contacts C-I…d_(z)^(2)[Pd]and C-I…d_(z)^(2)[Pt]can be attributed to the unconventional metal-involving halogen bonding;these contacts are among the strongest(4.30 and 5.42 kcal mol^(-1),correspondingly)between any metal center and iodine(Ⅰ)-based σ-hole donors.展开更多
基金supported by the Russian Foundation for Basic Research(project 20-03-00073,synthetic and crystal engineering studies)the Russian Science Foundation(project 21-73-00059,ELF,ED/ESP,AIM analyses)the MICIU/AEI from Spain for financial support of his computational studies(project number PID2020-115637GB-I00,FEDER funds,MEP,QTAIM and NCIplot analyses).
文摘Cocrystallization of the dithiocarbamate complexes[M(S_(2)CNEt_(2))_(2)](M=Ni 1,Pd 2,Pt 3)and X-substituted perfluoroarenes(X=I,Br;1,2-dibromoperfluorobenzene FBrB and 1,2-diiodoperfluorobenzene FIB)gives isomorphous cocrystals of(1-3)·2(FBrB)and 1·2(FIB),correspondingly,whose structures were studied by single-crystal X-ray diffractometry.The crystal structures demonstrate similar intermolecular contact types:short arene MS_(4)…π-hole stacking contacts,X…S halogen bonds,C-H…X(X=Br,I)bonds and C-H…F hydrogen bonds.In these structures,the{d_(z^(2))-M^(Ⅱ)S_(4)}moiety functions as an integrated five-center acceptor(that includes a metal d_(z^(2))-orbital,even for a poorly d_(z^(2))-nucleophilic Ni^(Ⅱ) center)toward theπ-hole of an X-substituted perfluoroarene.This interaction provides stacking of inorganic and organic units furnishing the reverse sandwich structures.Density functional theory(DFT)calculations,in combination with quantum theory of atoms-in-molecules(QTAIM)and noncovalent interaction plot(NCIplot)analyses,supported the structure-defining role of the{MS_(4)}…π-hole contacts.The nucleophilicity of the{MS_(4)}cores toward electron deficient π-holes was verified from the molecular electrostatic potential surface(MEP)and electron density/electrostatic potential(ED/ESP)profiles,and atoms-in-molecules(AIM)charge analysis.The relatively strong{MS_(4)}…π-hole contact strength(interaction energies for an{MS_(4)}…π-hole 1:1 adduct range from^(-1)2.1 to^(-1)3.5 kcal mol^(-1))is probably due to the large overlap between the electron deficient π-cloud and the integrated{MS_(4)}nucleophilic core.The 1:1 adduct based on 3 demonstrates the largest strength(13.5 kcal mol^(-1))in the series and this strength agrees well with the higher d_(z^(2))-nucleophilicity of the Pt^(Ⅱ) center revealed by the MEP analysis(-33.6 kcal mol^(-1)).
基金supported by the Russian Foundation for Basic Research(20-03-00073)Saint Petersburg State University for a postdoctoral fellowship.
文摘Co-crystallization of dithiocarbamate complexes[M^(Ⅱ)(S_(2)CNEt_(2))_(2)](M=Cu 1,Ni 2,Pd 3,Pt 4)and 1,3,5-triiodotrifluorobenzene(FIB)gives an isomorphic series of(1-4)·2FIB co-crystals exhibiting quadruple Cu/Ni/Pd/Pt isostructural exchange.In the structures of(1-4)·2FIB,the halogen-bonded C-I…M(Ni,Pd,Pt)and semicoordination M…I-C(Cu)metal-involving contacts were identified by X-ray diffractometry and their nature was verified theoretically.The directionality of the I_(σ-hole)…d_(z)^(2)M^(Ⅱ) and M^(Ⅱ)…I_(electron belt)interactions depends on the identity of a metal center:on going from a rather electrophilic Cu^(Ⅱ) to substantially more nucleophilic Ni^(Ⅱ),Pd^(Ⅱ),and Pt^(Ⅱ) centers,we observed the electron belt-to-σ-hole switch of a noncovalently bound iodine(I)of FIB and,correspondingly,its shift from semicoordination to halogen bonding.The negative values of the electrostatic potentials(given in parentheses)were estimated for all metal centers and they decrease in the order Cu^(Ⅱ)(-8.8)>Ni^(Ⅱ)(-24.5)>Pd^(Ⅱ)(-28.6)>Pt^(Ⅱ)(-33.3 kcal mol^(-1)).Despite the negative potentials at all M^(Ⅱ)s,the semicoordinative contact Cu…I was established by the recognition of the LP(I)→LP*(Cu)charge transfer using natural bond orbital(NBO)analysis and the comparison of electron density(ED)and electrostatic potential(ESP)minima positions along the I…Cu bond paths.In the case of the rather nucleophilic(although positively charged)Pd^(Ⅱ) and Pt^(Ⅱ) centers,the contacts C-I…d_(z)^(2)[Pd]and C-I…d_(z)^(2)[Pt]can be attributed to the unconventional metal-involving halogen bonding;these contacts are among the strongest(4.30 and 5.42 kcal mol^(-1),correspondingly)between any metal center and iodine(Ⅰ)-based σ-hole donors.
