US4024169A
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Titanium complexes with nitrogen
Assignee: Honeywell International Inc
•
Filing: 1975-11-28
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Granted: 1977-05-17
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Expires: 1995-11-28
Abstract
Abstract Complexes of the titanium cyclopentadienyl compound <IMAGE> and nitrogen, having the probable structure: <IMAGE> where the symbol N APPROX N represents a bonding state intermediate between the azo-N=N- bond and the hydrazine =N-N= bond; such complex having the simple dimeric form as indicated by molecular weight determination on this form dissolved in tetrahydrofuran, and having a polymeric form wherein a nitrogen atom of one molecule of the dimeric form is coordinated by a dative link with a Ti atom of another molecule of the dimeric form, as suggested by low solubility of this polymeric form in 1,2-dimethoxyethane and breakdown of this form to the dimeric form by action of tetrahydrofuran.
Inventors
- 👤 Guido P. Pez
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 18:58
CPC Classifications
C; C07; C07F; C07F17/00; C07F7/00; C07F7/28
Claims Analysis
Total Claims: 4
Claim 1
Independent Claim
270 words
Complex of the titanium cyclopentadienyl compound ##STR9## and nitrogen, having the structure: ##STR10## where the symbol N≈N represents a bonding state intermediate between the azo-N=N- bond and the hydrazine =N-N= bond; such complex having a cyclic dimeric form as indicated by molecular weight determination on this form dissolved in tetrahydrofuran, and having a polymeric form wherein a nitrogen atom of one molecule of the cyclic dimeric form is coordinated with a Ti atom of another molecule of the cyclic dimeric form as indicated by low solubility of this polymeric form in 1,2-dimethoxyethane and breakdown of this form to the cyclic dimeric form by action of tetrahydrofuran; said cyclic dimeric form of said complex showing molecular weight in tetrahydrofuran in good agreement with the theoretical value of 383 for such dimeric form, and having the following characteristic vibrational frequency assignments for the N 2 - related fundamentals: ______________________________________
Assignment Infrared Raman
______________________________________
cm.sup..sup.-1
cm.sup..sup.-1
N.sup.14 --N.sup.14
1296.0 1298, 1304
N.sup.15 --N.sup.15
1252.1 1259
Ti--N.sup.14 (anti-sym.)
581.4 579
Ti--N.sup.15 (anti-sym.)
566.4 565
Ti--N.sup.14 (sym.)
-- 526
Ti--N.sup.15 (sym.)
-- 509
______________________________________ said cyclic dimeric form of the complex being a red brown solid, stable for at least one day at room temperature as a solid and in solution in electron donor solvents; said polymeric form of said complex having the following characteristic infrared absorption peaks arising from N-N and Ti-N stretching vibrations: ______________________________________
Assignment Frequency (cm.sup..sup.-1)
______________________________________
N.sup.14 --N.sup.14
1221.9 ± 0.3
N.sup.15 --N.sup.15
1182.2 ± 0.3
Ti--N.sup.14 (anti-sym)
592.4 ± 0.3
Ti--N.sup.15 (anti-sym)
581.4 ± 0.5
______________________________________ said polymeric form being a black solid and being very sparingly soluble in 1,2-dimethoxymethane.
Claim 2
Dependent Claim
270 words
Complex of the titanium cyclopentadienyl compound ##STR9## and nitrogen, having the structure: ##STR10## where the symbol N≈N represents a bonding state intermediate between the azo-N=N- bond and the hydrazine =N-N= bond; such complex having a cyclic dimeric form as indicated by molecular weight determination on this form dissolved in tetrahydrofuran, and having a polymeric form wherein a nitrogen atom of one molecule of the cyclic dimeric form is coordinated with a Ti atom of another molecule of the cyclic dimeric form as indicated by low solubility of this polymeric form in 1,2-dimethoxyethane and breakdown of this form to the cyclic dimeric form by action of tetrahydrofuran; said cyclic dimeric form of said complex showing molecular weight in tetrahydrofuran in good agreement with the theoretical value of 383 for such dimeric form, and having the following characteristic vibrational frequency assignments for the N 2 - related fundamentals: ______________________________________
Assignment Infrared Raman
______________________________________
cm.sup..sup.-1
cm.sup..sup.-1
N.sup.14 --N.sup.14
1296.0 1298, 1304
N.sup.15 --N.sup.15
1252.1 1259
Ti--N.sup.14 (anti-sym.)
581.4 579
Ti--N.sup.15 (anti-sym.)
566.4 565
Ti--N.sup.14 (sym.)
-- 526
Ti--N.sup.15 (sym.)
-- 509
______________________________________ said cyclic dimeric form of the complex being a red brown solid, stable for at least one day at room temperature as a solid and in solution in electron donor solvents; said polymeric form of said complex having the following characteristic infrared absorption peaks arising from N-N and Ti-N stretching vibrations: ______________________________________
Assignment Frequency (cm.sup..sup.-1)
______________________________________
N.sup.14 --N.sup.14
1221.9 ± 0.3
N.sup.15 --N.sup.15
1182.2 ± 0.3
Ti--N.sup.14 (anti-sym)
592.4 ± 0.3
Ti--N.sup.15 (anti-sym)
581.4 ± 0.5
______________________________________ said polymeric form being a black solid and being very sparingly soluble in 1,2-dimethoxymethane.
Claim 3
Dependent Claim
32 words
A red-brown cyclopentadienyl titanium/dinitrogen complex of claim 1 in cyclic dimeric form having an infrared absorption peak attributable to N-N stretching at a frequency of about 1296 wavenumbers (cm - 1 ).
Claim 4
Dependent Claim
32 words
A black cyclopentadienyl titanium/dinitrogen complex of claim 1 in a polymeric form, having an infrared absorption peak attributable to N-N stretching at a frequency of about 1222 wavenumbers (cm - 1 ).
References Cited (Backward Citations)
US3776932A
Cited
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1980-05-16 | 1980-11-15 | 1981-05-17 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-05-16 | 1984-11-15 | 1985-05-17 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-05-16 | 1988-11-15 | 1989-05-17 | $7700.00 | Window Closed / Lapsed |