Welcome to the CentOS fora. Please see the recommended reading for new users linked in my signature.
I'd suggest you
chkconfig NetworkManager off, adjust the ifcfg files to have
NM_CONTROLLED="no" and try managing the network with the traditional
network service.
NetworkManager does not seem to do well with complex configurations.
If more help is needed then please
provide more information about your system by running "./getinfo.sh network" and showing us the output file.
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