Preparation and structural characterization of monoamine-monoamide bis(thiol) oxo complexes of technetium(V) and rhenium(V)

Journal Article · Wed Jan 19 00:00:00 EST 1994 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00080a022· OSTI ID:5109823

O'Neil, J P; Wilson, S R; Katzenellenbogen, J A ^[1]

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1. Univ. of Illinois, Urbana, IL (United States)

The authors report the design and synthesis of a novel N[sub 2]S[sub 2] ligand system for the formation of Re(V) oxo and [sup 99]Tc(V) oxo complexes. An S,S[prime]-bis(trityl) N-benzyl monoamine-monoamide (Bn-MAMA[prime]-Tr[sub 2]) complex was prepared in four steps from commercially available cysteamine hydrochloride. S-Trityl protection of cysteamine hydrochloride followed by N-acylation of the amine function with bromoacetyl bromide provided the corresponding primary bromide, which was then reacted with additional S-trityl-protected cysteamine to provide the S,S[prime]-bis(trityl) monoamine-monoamide ligand (MAMA[prime]-Tr[sub 2]). N-Alkylation by nucleophilic displacement with the methanesulfonate of benzyl alcohol gave the N-benzyl MAMA[prime] ligand in the thiol-protected form. Metal incorporation to provide the title compounds consisted of deprotection of the sulfur atoms with Hg(OAc)[sub 2] followed by H[sub 2]S to provide free bis(thiol) which could then be reacted with the corresponding metals in basic methanolic medium to provide a mixture of syn- and anti-substituted metal(V) oxo products (Bn-MAMA[prime]-M=O, metal = Re, [sup 99]Tc). The two disastereomers could be differentiated by proton NMR due to the upfield shifts of the methylene protons on the endo (anti) phenylmethyl substitutent (2.7 and 3.4 ppm) relative to those of the exo- (syn-) substituted isomer (4.7 and 5.1 ppm). An unambiguous structural assignment of the N-benzyl-MAMA-metal(V)-oxo compounds was established by an X-ray diffraction study on the rhenium compounds 8a-Re (syn) and 8b-Re (anti).

• DOE Contract Number: FG02-86ER60401
• OSTI ID: 5109823
• Journal Information: Inorganic Chemistry; (United States), Vol. 33:2; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
RHENIUM COMPLEXES
STRUCTURAL CHEMICAL ANALYSIS
TECHNETIUM COMPLEXES
AMIDES
AMINES
CHEMICAL PREPARATION
NUCLEAR MAGNETIC RESONANCE
OXIDES
TECHNETIUM 99
THIOLS
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
CHALCOGENIDES
COMPLEXES
HOURS LIVING RADIOISOTOPES
INTERMEDIATE MASS NUCLEI
INTERNAL CONVERSION RADIOISOTOPES
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
MAGNETIC RESONANCE
NUCLEI
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXYGEN COMPOUNDS
RADIOISOTOPES
RESONANCE
SYNTHESIS
TECHNETIUM ISOTOPES
TRANSITION ELEMENT COMPLEXES
YEARS LIVING RADIOI
400201* - Chemical & Physicochemical Properties