Lindeman

Crystallographic Feedback to Chemistry – Beyond just Pictures: 

Crystallographic Feedback to Chemistry – Beyond just Pictures Dr. Sergey V. Lindeman Marquette University Milwaukee, WI

“Sergey – who?!”re-introducing self: 

“Sergey – who?!” re-introducing self 1975-1980 Chemistry Department, Moscow State University, student. 1977-1980 Struchkov’s Lab, INEOS RAN, night-shift technician. 1980-1994 Struchkov’s Lab, INEOS RAN, probationer, junior researcher, senior staff member 1988 Struchkov’s Lab, INEOS RAN, PhD degree

Slide3: 

Back in USSR… Steroid hormones/medicines Polymers/oligomers Clathrates Inclusion compounds Pharmaceuticals; Natural compounds High-energy molecules Macrocyclic complexes of (post)transition metals

Norway 1994-1996: 

Norway 1994-1996 -Complexes of Dihalogens Coordinationally unsaturated compounds

Texas 1996-2005: 

Texas 1996-2005 Reaction intermediates Molecular wires Charge-Transfer Complexes, Topochemical reactions

Messing-up with proteins…: 

Messing-up with proteins… High-resolution (~0.9 Å) endonuclease structure

Marquette2005 – now: 

Marquette 2005 – now

The very new old reciprocal world: 

The very new old reciprocal world The very first X-ray diffraction image of a crystal structure – [Cu(SO4)·5H2O] (from the Nobel Lecture of Max von Laue, 1914) and a very modern X-ray diffractometer with CCD camera (Bruker-AXS; 2006)

and about Numbers…: 

and about Numbers… 1977-1994 250 structures 1994-1996 ~50 structures 1996-2004 ~450 structures 2005-2007 (20 months) ~550 structures ~200 publications (1977-1997)

and more about Numbers…: 

and more about Numbers… ISI's 10858 Most Cited Chemists, 1981-June 1997, ranked by total citations: Author name averag total total cites articles cites 1. BAX A 142.47 152 21655 2. POPLE JA 79.80 176 14044 3. SCHLEYER PV 25.83 525 13559 4. ERNST RR 71.81 182 13069 5. WHITESIDES GM 38.71 318 12310 6. SCHAEFER HF 23.15 515 11921 7. HUFFMAN JC 20.20 577 11654 8. RHEINGOLD AL 13.63 830 11317 9. SEEBACH D 32.31 349 11275 10. LEHN JM 35.25 307 10823 11. MEYER TJ 39.29 267 10490 12. SMALLEY RE 108.92 96 10456 13. BARD AJ 31.13 333 10365 14. TRUHLAR DG 31.43 328 10310 15. STEWART JJP 261.00 39 10179 16. COREY EJ 33.43 303 10129 17. YAMAMOTO Y 10.70 935 10007 18. TANAKA T 10.44 954 9961 19. COTTON FA 15.63 634 9911 20. TANAKA K 8.17 1202 9820 54. SHELDRICK GM 16.90 441 7453 ........ 68. STRUCHKOV YT 4.14 1651 6841 ....... 97. KOCHI JK 28.49 214 6096 ....... 442. KOCHETKOV NK 8.37 392 3280 ....... 898. ZEFIROV NS 5.09 465 2366 ....... 4045. ANTIPIN MY 3.08 320 985 ....... 4203. SHKLOVER VE 4.39 219 962 .......

and more…: 

and more…

Slide12: 

Publications (1997-2005) J.Am.Chem.Soc. – 12 Angew. Chem. – 7 J.Org.Chem. – 6 J.Chem.Soc. Perkin 2 – 5 New J. Chem. – 2 Chem.Commun. – 2 Organometallics – 2 Coord.Chem.Rev. – 1 Others – 3

Slide13: 

In-situ Crystallization and X-ray Structures of Benzene·Br2 and Toluene·Br2 Molecular Complexes Classical intermediates of electrophilic bromination Aggressive reactionable liquids Sensitive to light and metals Melting points below -30C Phase transition disorder → order at -70C Twinning (non-regular) Large absorption (μ ~ 100 cm-1) Capillary effects Different from Hassel & Srømme structure Final e.s.d. for C-C bonds  = 0.006 Å Published in New J. Chem. 2002, 26, 589 (A.Vasilyev, S.Lindeman, J.Kochi)

Slide14: 

Non-Centrosymmetric Charge-Transfer Diamondoid Networks CBr4/Hal- -complexes Sphaleroid structural type Intrinsically non-centrosymmetric (I-4) Structurally adjustable Easily formed (high-school student practice) Phase-matchable second harmonics generation comparable with that of LiNbO3 S. Lindeman, J. Hecht, J. Kochi JACS, 2003, 125, 11597

Slide15: 

Specific Binding of Alkali Ions to Arene Donors Original idea – Dr. R. Rathore (Na+) Decisive crystallization – Dr. G. Fukin (K+, Rb+, Cs+) Anomalous M+ binding to benzene ring Biological interest G. Fukin, S. Lindeman, J. Kochi JACS, 2002, 124, 8329.

Slide16: 

Guys, I have been missing you every single day since I left the Lab! The End