The Two Bioinorganic Projects of Research Methodology Fall 2012 Ligand Synthesis Complex Synthesis Biochemical Studies Tetraphenyl porphyrin Pteridinyl.

The Two Bioinorganic Projects of Research Methodology Fall 2012

Ligand Synthesis

Complex Synthesis

Biochemical Studies

Tetraphenyl porphyrinPteridinyl

phenanthroline

DPPZ L-allox L-amino L-keto L-UN

Types of Pteridinyl Phenanthroline Ligands (and other)

Pteridinyl phenanthroline synthesis

in NaOH pH ~11

MeOH

20 h or so

Ligand Synthesis

(by Alexandra)

General Description of Ligand Synthesis

Group and Ligand Assignments for Synthesis and Characterization Group # Students ligand

complexGroup 1 — Linda Cho, Katie Guye DPPZ

[Ru(bpy)2(DPPZ)](PF6)2

Group 2 — Rachael Kahlin,Julia Heer L-allox[Ru(bpy)2(L-allox)](PF6)2

Group 3 — Julie Han,Bingqing Li L-amino[Ru(bpy)2(L-amino)](PF6)2

Group 4 — Alicia Makepeace,Misha Sims L-keto[Ru(bpy)2(L-keto)](PF6) Group 5 — Terry Huh,Maria Nam L-keto

[Ru(bpy)2(L-keto)](PF6)2

Group 6 — Anna Kalinsky,Janielle Vidal L-keto (to make L-aap)[Ru(bpy)2(L-aap)](PF6)2 Group 7— Chloe Baumann,Sara Kim L-UN (to make L-alap)[Ru(bpy)2(L-alap)](PF6)2 ‘Group’ 8 — Alexandra Kirsch L-tallox (thioalloxazine) [Ru(bpy)2(L-tallox)](PF6)2

DPPZ L-allox L-amino L-keto

L-aap L-alap

L-UN

w/ Ru w/ Ru

Group and Ligand Assignments for Synthesis and Characterization Group # Students ligand

complexGroup 1 — Linda Cho, Katie Guye DPPZ

[Ru(bpy)2(DPPZ)](PF6)2

Group 2 — Rachael Kahlin,Julia Heer L-allox[Ru(bpy)2(L-allox)](PF6)2

Group 3 — Julie Han,Bingqing Li L-amino[Ru(bpy)2(L-amino)](PF6)2

Group 4 — Alicia Makepeace,Misha Sims L-keto[Ru(bpy)2(L-keto)](PF6) Group 5 — Terry Huh,Maria Nam L-keto

[Ru(bpy)2(L-keto)](PF6)2

Group 6 — Anna Kalinsky,Janielle Vidal L-keto (to make L-aap)[Ru(bpy)2(L-aap)](PF6)2 Group 7— Chloe Baumann,Sara Kim L-UN (to make L-alap)[Ru(bpy)2(L-alap)](PF6)2 ‘Group’ 8 — Alexandra Kirsch L-tallox (thioalloxazine) [Ru(bpy)2(L-tallox)](PF6)2

DPPZ L-allox L-amino L-keto L-UN

Phenylenediamine

5,6 –diamino2,4 dihydroxy pyrimidine

4,5,6 –triamino pyrimidine

5,6 –diamino4-hydroxy pyrimidine

5,6 –diamino pyrimidine

True or false?

Blood is red because of the iron in hemoglobin.

“Red blood cells”A close-up of red bloodcells within a capillary.

Over 99 percentof the blood vessels in the

body are capillaries,even though they only hold 5 percent of the body’s blood.

Falsepor·phy·rin

Function: nounEtymology: from Greek porphyra purple

-any of various compounds with a macrocyclic structure that consists essentially of four pyrrole rings joined by four =CH- groups; especially : one (as chlorophyll or hemoglobin) containing a central metal atom and usually exhibiting biological activity

Protoporphyrin IX

Glycine +Succinyl CoA

the pyrrole ring is formed

Nature’s synthesis of Porphyrin

The Adler synthesis of simple, symmetrically substituted porphyrins:

Meso position

R = phenyl (TPP) toluyl (TTP) p-chlorophenyl (TClPP)

Ligand Synthesis: Condensations are a Theme

Schiff-Base Ligands

(Thanks, Eesha….)