Influence of structural and electronic properties of organomolybdenum(ii) Supporting Information

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1 Electronic Supplementary Material (ESI) for Catalysis Science & Technology. This journal is The Royal Society of Chemistry 2015 Influence of structural and electronic properties of organomolybdenum(ii) compounds of the type [CpMo(CO) 3 R] and [CpMo(O 2 )(O)R] (R = Cl, CH 3, CF 3 ) on the catalytic oxidation of olefins Simone A. Hauser, a Robert M. Reich, a János Mink, b,c Alexander Pöthig, d Mirza Cokoja d and Fritz E. Kühn a,e * a Molecular Catalysis, Department of Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, D Garching bei München, Germany. Tel: ; Fax: Corresponding author: fritz.kuehn@ch.tum.de b Hungarian Academy of Sciences, Chemical Research Center, Pusztszeri u , 1025 Budapest, Hungary c Faculty of Information Technology, University of Pannonia, Egyetem u Veszprém, Hungary d Catalysis Research Center, Technische Universität München, Ernst-Otto-Fischer-Straße 1, D Garching bei München, Germany e Chair of Inorganic Chemistry, Department of Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, D Garching bei München, Germany These authors contributed equally to this work. Table of Contents Supporting Information S1. X-Ray single crystallography Table S.1.Crystallographic data for compounds 3 and 6. S2. Computational results - Visualization, coordinates and energies Figure S2.1.LUMOs of the compounds [CpMo(CO) 3 R] Table S2.1.Summary of computational results S2.2 Calculated coordinates for [CpMo(CO) 3 Cl] (1) S2.2 Calculated coordinates for [CpMo(CO) 3 CH 3 ] (2) S2.2 Calculated coordinates for [CpMo(CO) 3 CF 3 ] (3) S3. Experimental and calculated fundamental frequencies and force constants Table S3.1. Experimental and calculated fundamental frequencies for [CpMo(CO) 3 CH 3 ] and [CpMo(CO) 3 CD 3 ]. Table S3.2. Calculated force constants for [CpMo(CO) 3 CH 3 ] and [CpMo(CO) 3 CD 3 ]. Table S 3.3 IR and Raman frequencies assigned to the spectroscopic modes of vibration for the complexes 1 3 and 2a. S1

2 S1. X-Ray single crystallography Data were collected on an X-ray single crystal diffractometer equipped with a CCD detector (APEX II, CCD), a fine-focused sealed tube with MoK radiation ( = Å) and a graphite monochromator, by using the APEX2 software package. [1] The measurements were performed on single crystals coated with perfluorinated ether. The crystals were fixed on the top of a glass fiber and transferred to the diffractometer. Crystals were frozen under a stream of cold nitrogen. A matrix scan was used to determine the initial lattice parameters. Reflections were merged and corrected for Lorenz and polarization effects, scan speed, and background using SAINT. [2] Absorption corrections, including odd and even ordered spherical harmonics were performed using SADABS. [2] Space group assignments were based upon systematic absences, E statistics, and successful refinement of the structures. Structures were solved by direct methods with the aid of successive difference Fourier maps [3], and were refined against all data using the APEX 2 software [1] in conjunction with SHELXL-97 [5] and SHELXLE [6]. Methyl hydrogen atoms were refined as part of rigid rotating groups, with a C H distance of 0.98 Å and U iso(h) = 1.5 U eq(c). Other H atoms were placed in calculated positions and refined using a riding model, with methylene and aromatic C H distances of 0.99 and 0.95 Å, respectively, and U iso(h) = 1.2 U eq(c). If not mentioned otherwise, non-hydrogen atoms were refined with anisotropic displacement parameters. Fullmatrix least-squares refinements were carried out by minimizing Σw(F o2 -F c2 ) 2 with SHELXL- 97 [5] weighting scheme. Neutral atom scattering factors for all atoms and anomalous dispersion corrections for the non-hydrogen atoms were taken from International Tables for Crystallography. [4] Images of the crystal structures were generated by PLATON. [7] References: [1] APEX suite of crystallographic software. APEX 2 Version Bruker AXS Inc., Madison, Wisconsin, USA (2008). [2] SAINT, Version 7.56a and SADABS Version 2008/1. Bruker AXS Inc., Madison, Wisconsin, USA (2008). [3] Sheldrick, G. M. "SHELXS-97", Program for Crystal Structure Solution, Göttingen, (1997). [4] International Tables for Crystallography, Vol. C, Tables (pp ), (pp ), and (pp ), Wilson, A. J. C., Ed., Kluwer Academic Publishers, Dordrecht, The Netherlands, [5] Sheldrick, G. M. "SHELXL-97", University of Göttingen, Göttingen, Germany, (1997). [6] Huebschle, C. B., Sheldrick, G. M. & Dittrich, B. SHELXLE, J. Appl. Cryst. 2011, 44, [7] Spek, A. L. "PLATON", A Multipurpose Crystallographic Tool, Utrecht University, Utrecht, The Netherlands, (2010). S2

3 Table S.1.Crystallographic data for compounds 3 and CCDC formula C 9 H 5 F 3 MoO 3 C 6 H 5 F 3 MoO 3 fw colour/habit clearlight yellow needle Intense yellow fragment Cryst dimensions (mm 3 ) crystsyst triclinic monoclinic spacegroup P 1 C 2/c a, Å (2) (3) b, Å (2) (1) c, Å (2) (2) α, deg (1) 90 β, deg (1) (1) γ, deg (1) 90 V, Å (14) (4) Z 1 8 T, K 123(2) 123(2) D calcd, g cm μ, mm F(000) θ range, deg Index ranges (h, k, l) 7, 7, 0 8 ±24, ±8,±14 no. of rflns collected no. of indep rflns/r int 910/ / no. of obsd rflns (I>2σ(I)) no. of data/restraints/params 910/3/ /0/118 R1/wR2 (I>2σ(I)) a / / R1/wR2 (all data) a / / GOF (on F 2 ) a Largest diff peak and hole (e Å -3 ) / / a R1 = ( F o - F c )/ F o ; wr2 = { [w(f o2 -F c2 ) 2 ]/ [w(f o2 ) 2 ]} 1/2 ; GOF = { [w(f o2 -F c2 ) 2 ]/(n-p) 1/2 S3

4 S2. Computational results - Visualization, coordinates and energies Figure S2.1.LUMOs of the compounds [CpMo(CO) 3 R] with R = Cl (1), CH 3 (2) and CF 3 (3) (from left to right) in gas phase (B3LYP/6-31+G**(d,p) level of theory. Table S2.1.Summary of computational results compounds Mulliken charge on Mo HOMO-LUMO-gap [ev] Sum of electronic and thermal Enthalpies [ev] Sum of electronic and thermal Free Energies [ev] Mo-Ligand-Polarity S4

5 S2.2 Calculated coordinates for [CpMo(CO) 3 Cl] (1) C H C C H C H C H H O O O C C C Mo Cl S5

6 S2.3 Calculated coordinates for [CpMo(CO) 3 CH 3 ] (2) C H C C H C H C H H O O O C C C Mo C H H H S6

7 S2.4 Calculated coordinates for [CpMo(CO) 3 CF 3 ] (3) C H C C H C H C H H O O O C C C Mo C F F F S7

8 S3. Experimental and calculated fundamental frequencies and force constants Table S3.1. Experimental and calculated fundamental frequencies for [CpMo(CO) 3 CH 3 ] and [CpMo(CO) 3 CD 3 ]. [CpMo(CO) 3 CH 3 ] [CpMo(CO) 3 CD 3 ] Potential Energy Distribution d Description Exper. Calcd. Exper. Calcd. (%) of mode A a ν s CO + 10 ν s MoC CO sym. stretching ν a CO + 11 ν a MoC CO asym. stretching s MoCO + 25 a MoCO c + 8 s CMoC MoCO bending a MoCO + 21 s MoCO + ν s MoC MoCO bending ν s MoC +14 a MoCO + 13 ν a MoC MoC stretching a MoCO + 15 ν s MoC + 10 νmocp MoCO bending ν a MoC + 22 a MoCO + 12 νmocp MoC stretching νmo-me + 17 ν a MoC+ 9 ν s MoC Mo-Me stretching νmocp + 10 s MoC +5 νmo-me Mo-Cp stretching b s CpMoMe + 13 CMoCp + 10 MoCO CpMoMe deformation s MoC CMoCp MoC 3 sym. deformation a CMoC + 32 a CMoCp + 16 CpMoMe CMoC deformation 13 ~60 66 ~ CMoCp + 26 CpMoMe CMoCp deformation A ν a CO + 8 ν a MoC CO asym. stretching a MoCO + 6 a CMoCp MoCO deformation ν a MoC + 11 a MoCO + 6 ν a CO MoC stretching a MoCO + 19 a CMoC + 9 s MoCO MoCO deformation a MoCO + 5 ν a CO + 4 a CMoC MoCO deformation a CMoMe + 43 a CMoC CMoMe deformation ~ CMoCp + 5 a MoCO CMoCp deformation a CMoC + 21 a MoCO CMoC deformation a Averaged IR and Raman frequencies were used as fundamentals when the wavenumbers were slightly different or split due to the solid-state effects. b Experimental frequencies below 150 cm -1 were assigned on the basis of normal coordinate calculations. c The (MoCO) are the linear bendings of Mo-C-O groups in the plane of CMoCp, the notation of (MoCO) requests the linear bendings perpendicular to the plane of CMoCp. d Potential Energy Distributions (PED) were taken from the result of [CpMo(CO) 3 CH 3 ] calculations. S8

9 Table S3.2. Calculated force constants for [CpMo(CO) 3 CH 3 ] and [CpMo(CO) 3 CD 3 ]. Force constants Groups involved and descriptions Numerical values of force constants Units K 1 (C O) C O opposite to CH 3 /CD a K 2 (CO) CO close to CH 3 /CD a F s (CO,CO) Interaction between CO, CO groups a F l (C O,CO) Interaction between C O,CO groups a K(MoC) Mo-CO a F(MoC,MoC) Mo-CO a K(Mo-Me) Mo-CH 3, Mo-CD a K(Mo-Cp) Mo-Cp a H(MoCO) MoCO linear bending (in plane) b h(moco,moco) MoCO, MoCO interaction b H (MoCO) MoCO linear bending (out of plane) b h (MoCO,MoCO) MoCO, MoCO interaction 0 b H(CMoMe) skeletal bending (0.55) c b H(CMoC) skeletal bending (0.62) b H(CMoCp) skeletal bending (0.48) b H(CpMoMe) skeletal bending (0.50) b F(MoMe,MoC ) stretch-stretch interaction (0.10) a F(MoMe,MoC) stretch-stretch interaction (0.05) a Units of force constants are: a, 10 2 N m -1 ; b, N m rad -2 ; c, The constrained values are listed in brackets. S9

10 Table S 3.3 IR and Raman frequencies assigned to the spectroscopic modes of vibration for the complexes 1 3 and 2a [CpMo(CO) 3 CD 3 ] a 3 IR Raman IR Raman IR Raman IR Raman Assignment 3123m 3127m 3113m 3123m 3113m 3123m 3126m 1303m v s (CH), Cp 3118m v a (CH), Cp 3103m 3111w 3100w 3102w 3108w v a (CH), Cp 2981m 2982m 2233m 2236m v a (CH 3 /CD 3 ) 2902m 2905m 2116m 2114m v s (CH 3 /CD 3 ) 2020w,sh 2019m 2018w,sh 2018m v s (C O) 2060w,sh 2056m v s (C O) 2040vs 2041vs 2006s 2003s 2004s 2002s 2048s 2042s v s (C O) 1974w 1948w,sh 1945w,sh 1980w,sh 1977s v a (C O) 1969vs 1960s 1920m,sh 1921s,sh 1920m,sh 1920s,sh 1963s 1962vs v a (C O) 1949vs v a (C O) 1932vs 1930m 1903vs 1900vs 1901vs 1889vs 1934vs 1932s v a (C O) 1924s,sh 1916m,sh v a (C O) 1421m 1422vw 1423m 1425m 1423m 1421m,b 1430m 1427m v a (CC), Cp 1423m 1420m 1062m 1061m δ a (CH 3 /CD 3 ) 1354w 1355vw 1354w 1352w 1353w 1352w 1356w v a (CC), Cp 1161m 883m 881s δ s (CH 3 /CD 3 ) 1110vw 1109s 1109vw 1107s 1109vw 1107s 1113vw 1109s v s (CC), Cp 1064m 1061m 1060m 1061m 1062m 1061m 1069m β(ch), Cp 1050s 1057m v a (CF 3 ) 1043s v a (CF 3 ) 1014m 1011m 1011vw 1012m 1009vw 1012s β(ch), Cp 1005m 1007vw 1003vw 1004s 1005vw β(ch), Cp 982s 978vw v s (CF 3 ) 822s 816vw 825s 822vw 822s 821vw 831m 827m γ(ch), Cp 695m 692m ρ s (CF 3 ) 613w 608vw 488vs ρ(ch 3 /CD 3 ) 475s 475s ρ(ch 3 /CD 3 ) 601w ~600vw 613w 608vw 614w,sh 613w δ s (MoCO) 561s 560vw 587s 584vw 597s 596w 573s 571w δ s (MoCO) 524s ~520vw 562vs 562m 561vs 563vw 546vs 544w β a (MoCO) 755w 758vw 548s,sh 549vw ρ(ch 3 /CD 3 ) 525w 521w δ a (CF 3 ) 512w δ a (CF 3 ) 471s 464w 502w,sh 498m,sh 498w,sh 479s 477w v s (MoC) 471s 464w 489vs 482m 488vs 490w,sh 479s 477w γ a (MoCO) 465w,sh 463w,sh 476ms 455ms 458ms β a (MoCO) 432w 428vw β a (MoCO) 432w 428vw 451s 453m 448s 451s 430vs 432m v a (MoC) 415m 420vw 437m 438vs 429ms 429s 404m 402m γ(moco) 405w 408ms 392m 391m v(moc), CH 3 /CD 3 383w,sh v a (MoCp), tilt 371m 355w 355s 353m 352vs 366w 361w,sh v a (MoCp), tilt 361s a 350w,sh 335w 334vs 334w 333vs v s (MoCp) 337vw a 338ms 352vw 350vs v s (MoCp) 281vs a 278w v(mocl) 251s 249s v(moc), CF 3 234m 233m ρ(cf 3 ) 173s 125vw,sh 160s τ(ch 3 /CD 3 ) 160m 148m τ(ch 3 /CD 3 ) 130w,sh 133w 130w,sh 137w 137w,m δ(cpmor) 107w 104w 119w 119w δ s (CMoC) 106vw δ s (CMoC) 90w,sh 90w,sh δ a (CMoC) 60vw 60vw δ(cmocp) a Far infrared data taken from ref. 25 b Notation of fundamental modes: ν stretching; δ bending or deformation; ρ rocking; β in plane, γ out of plane deformation; τ torsion; subscript s symmetric, subscript a anti-symmetric. S10