had to do a bunch of research on this, but it does work, once config'd correctly.

using Apache/2.2.3 (Win32) mod_ssl/2.2.3 OpenSSL/0.9.8b 
PHP PHP Version 5.1.5-dev

ldap_bind was getting "81 Can't contact LDAP server" which was really annoying, since the connection worked fine without "ldaps"
using:

$ldapconnect = @ldap_connect( $connection_string );

well, actually the bind was really the one failing...

$bind = ldap_bind($ldapconnect, $client, $this->objSecurityLogin->Password);

many attempts to determine until i smartened up and turned on the trace level:

ldap_set_option(NULL, LDAP_OPT_DEBUG_LEVEL, 7);

which must go before the connect!

found that on windows, you can't specifiy a quote in the ldap.conf:
i had:
TLS_REQCERT never
TLS_CACERT "C:\\Documents\\Tools\\Apache2\\conf\\ssl\\ad.pem"
which throws the error..
TLS: could not load verify locations (file:`"C:\Documents\Tools\Apache2\conf\ssl\ad.pem"',dir:`').
TLS: error:0200107B:system library:fopen:Unknown error .\crypto\bio\bss_file.c:122
TLS: error:2006D002:BIO routines:BIO_new_file:system lib .\crypto\bio\bss_file.c:127
TLS: error:0B084002:x509 certificate routines:X509_load_cert_crl_file:system lib .\crypto\x509\by_file.c:274
ldap_err2string

changed to:
TLS_REQCERT never
TLS_CACERT C:\\Documents\\Tools\\Apache2\\conf\\ssl\\ad.pem 
which cleans it up as:
TLS trace: SSL_connect:before/connect initialization
TLS trace: SSL_connect:SSLv2/v3 write client hello A
TLS trace: SSL_connect:SSLv3 read server hello A
TLS certificate verification: depth: 1, err: 0, subject: /DC=xxx/DC=yyy/CN=zzzz, issuer: /DC=abab/DC=yyy/CN=zzzz
TLS certificate verification: depth: 0, err: 0, subject: ......

so the moral to the story is even though PHP wants quotes in some windows config parms, it won't work if its in ldap.conf!