TY - JOUR

T1 - Metal-involving halogen bond Ar-I⋯[d: Z 2PtII] in a platinum acetylacetonate complex

AU - Rozhkov, Anton V.

AU - Ivanov, Daniil M.

AU - Novikov, Alexander S.

AU - Ananyev, Ivan V.

AU - Bokach, Nadezhda A.

AU - Kukushkin, Vadim Yu

PY - 2020/1/21

Y1 - 2020/1/21

N2 - A combined XRD and theoretical study for two adducts, [Pt(acac)2]·2(1,3,5-FIB) and [Pd(acac)2]·1,3,5-FIB (Hacac = acetylacetone; 1,3,5-FIB = 1,3,5-triiiodotrifluorobenzene), reveals that differences in the type formed halogen bond (XB) depend on the identity of the metal center. Only [Pt(acac)2] forms rare two-center metal-involving XB Ar-I⋯[dz2PtII] (where the positively charged PtII center acts as a nucleophile toward an iodine σ-hole), while three-center bifurcated XB I⋯η2(O,O) was detected in both adducts. The observed linkage Ar-I⋯[dz2PtII] provides an experimental argument favoring the previously established (by a kinetic study) XB-formation step upon oxidative addition of I2 to [Pt(acac)2]. The variable temperature XRD study of [Pt(acac)2]·2(1,3,5-FIB) (100-300 K; five XRD experiments) demonstrates that the I⋯Pt and I⋯O contacts weaken simultaneously on heating that allows the consideration of the Pt1-O2 bond as an integrated XB acceptor. Appropriate DFT calculations (M06/DZP-DKH level of theory) performed by single-point "quasi-solid state" calculations with topological analysis of the electron density distribution within the framework of the Bader theory (QTAIM method), confirmed the existence of the two-center metal-involving XB I⋯Pt in the structure of [Pt(acac)2]·2(1,3,5-FIB) and three-center I⋯η2(O,O) bifurcated XBs for both adducts. All these interactions exhibit a non-covalent nature with estimated energies in the range of 2.1-4.3 kcal mol-1.

AB - A combined XRD and theoretical study for two adducts, [Pt(acac)2]·2(1,3,5-FIB) and [Pd(acac)2]·1,3,5-FIB (Hacac = acetylacetone; 1,3,5-FIB = 1,3,5-triiiodotrifluorobenzene), reveals that differences in the type formed halogen bond (XB) depend on the identity of the metal center. Only [Pt(acac)2] forms rare two-center metal-involving XB Ar-I⋯[dz2PtII] (where the positively charged PtII center acts as a nucleophile toward an iodine σ-hole), while three-center bifurcated XB I⋯η2(O,O) was detected in both adducts. The observed linkage Ar-I⋯[dz2PtII] provides an experimental argument favoring the previously established (by a kinetic study) XB-formation step upon oxidative addition of I2 to [Pt(acac)2]. The variable temperature XRD study of [Pt(acac)2]·2(1,3,5-FIB) (100-300 K; five XRD experiments) demonstrates that the I⋯Pt and I⋯O contacts weaken simultaneously on heating that allows the consideration of the Pt1-O2 bond as an integrated XB acceptor. Appropriate DFT calculations (M06/DZP-DKH level of theory) performed by single-point "quasi-solid state" calculations with topological analysis of the electron density distribution within the framework of the Bader theory (QTAIM method), confirmed the existence of the two-center metal-involving XB I⋯Pt in the structure of [Pt(acac)2]·2(1,3,5-FIB) and three-center I⋯η2(O,O) bifurcated XBs for both adducts. All these interactions exhibit a non-covalent nature with estimated energies in the range of 2.1-4.3 kcal mol-1.

KW - ZETA BASIS-SETS

KW - OXIDATIVE-ADDITION

KW - NONCOVALENT INTERACTIONS

KW - MECHANISTIC PATHWAYS

KW - CRYSTAL-STRUCTURE

KW - ARYL HALIDES

KW - IODINE

KW - CENTERS

KW - PD

KW - KINETICS

UR - http://www.scopus.com/inward/record.url?scp=85078204265&partnerID=8YFLogxK

UR - http://www.mendeley.com/catalogue/metalinvolving-halogen-bond-arid-z2-pt-ii-platinum-acetylacetonate-complex

U2 - 10.1039/c9ce01568j

DO - 10.1039/c9ce01568j

M3 - Article

AN - SCOPUS:85078204265

VL - 22

SP - 554

EP - 563

JO - CrystEngComm

JF - CrystEngComm

SN - 1466-8033

IS - 3

ER -